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From: The Fasting Game (Fasting Log) -- Everyone is Welcome to Join at any Time
Days since inception: 1011 Current Fasting Period Points: 1 Longest Point Streak: 6 Total Food Days: 270 Total Fasting Points: 741
Average Exercise During Current Session: exercise time keeps being erratic, I got in a good four and a half hours of exercise yesterday
First Recorded Weight (lbs.): 163.5 Total Days since Recording Weight: 981 Current Weight (lbs.): 132.3 Total Weight lost (lbs.): 31.2
Weight lost during current session (lbs.): -3.9 Most weight lost during a session (lbs.): 5.1 Points of that session: 3 Current BMI: 18.5
Maintaining weight through a set minimum weight of 130.0 lbs., under 130.0 lbs. during my daily weigh time shall turn the next day into a food day.
When it requires more than three fasting days to drop my weight under the set maintenance weight, I will fast an extra day to reduce the weight drift.
Favorite beverage: A bottle of water with fruit punch flavored zipfizz, a teaspoon of creatine and greens powder, lemon juice, local honey, and nutmeg.
Thoughts on maintenance weight: Seems like I have a goldilocks zone that pivots around 131.0 to 131.5 lbs. as a set maintenance weight. When my weight goes over my muscles buff up with the most noticeable gains being in my chest, upper arms, and hips while maintaining a nice waist. When i drop under my mid-section drops weight the fastest but although I continue to have a good figure my chest pays the price as my ribcage pokes through. Ideal goldilocks zone = BMI 18.2 last fasting day, 18.8 food day. Since I've dropped my set maintenance weight to 130.0 lbs., I'll have to wait to see what happens.
Link to my fasting log spreadsheet: https://docs.google....dit?pli=1#gid=0. Feel free to duplicate/copy it to log your own stats. It compares periods
I've created a fun and easy to do at home youtube exercise video thread in the exercise section of lop at: https://www.myproana...-make-your-own/.
I doubt my weight will drop low enough by morning to turn tomorrow into another emergency food day in order to maintain weight, but I did manage to put in the same workout routines as before and worked with the exercise ball as well as stretches that I have difficulties with. My resolve in being able to stretch and extend all the ways I've never been able to ever do before remains high. I just want to know what it feels like to have a body that has full range of motion in every way possible. I did prepare a pizza just incase my weigh in tomorrow surprises me, but if it doesn't I'll just have it the day after tomorrow. The pizza will be just as crisp and as good either way, as I've done that before. This morning's stats came in at a height of 5'11", weight of 132.3 lbs., 11.4 lbs. body fat at 8.6%, 66.9% water mass, 7.1% bone mass, 23" waist circumference and 25" abdominal circumference with a normal 2" separation between the two mid-section circumference measurements indicating a bloated state of being. Once more I put in two and a half hours of work out time in the evening. In addition I got in around an two hours of youtube video exercises. From now on, as long as I'm doing exercise videos, I'll claim a daily average of four and a half hours of daily exercise per session on my spreadsheet.
All the dishes from first feeding emptied by the time second feeding came around, and I didn't see who actually was here for first feeding. At second feeding the mother of two kits and her kits and another large raccoon was here. The two kits are adorable, and the mother is one that I used to feed apple pie by hand all the time. I made sure she got apple pie. One of the kits just came over to play with my sock. Everyone is now either eating or playing. Their voices are shill, kind of high pitched sounds which seem happy to me. I won't stay out long tonight, just want to see if the family of four kits come. They normally are here by now.
Source: The Fasting Game (Fasting Log) -- Everyone is Welcome to Join at any Time


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The Love Canal is located near Niagara Falls in upstate New York. The Canal was constructed as a waterway during the nineteenth century, but was abandoned shortly afterwards. The Love Canal story is essentially the story of the thousands of families who lived unknowingly amongst an abandoned toxic chemical waste dump. It wasn't the first time in U.S history where this has happened, nor was it the worst, but it did grab the public's attention. In the 1930's before the Love Canal area was turned into
Love Canal When one thinks about an environmental disaster, the image of a large explosion in a highly industrial area comes to mind. Such is not the case in the Love Canal emergency. Unlike most environmental disasters, the events of Niagara Falls's Love Canal weren't characterized by a known and uncontrollable moment of impact. It developed over a period of several decades, since the effects of leaching chemicals is uncertain and slow in development and the visual effects are very limited
was place underground near homes and schools. A mother, Louis Gibbs who lived near the Love Canal said, " When I brought this American dream home my son was one and very healthy. Then he started to get very ill and experiences some liver problems, asthma, and then epilepsy. I could not understand, they came one after another, until I read a series written by Mr. Michael Brown, who explained that the Love Canal has toxic waste underneath the neighborhood school and it leaches in resident homes." She
Love Canal is a controversial environmental tragedy. Although, Love Canal is not as big as the recent Freedom Industry spill in West Virginia or China's toxic air pollution, the Love Canal even continues to be debated because more and more information about its causes and harms is revealed each decade since 1953. The case of Love Canal is interesting, because toxic dumping wasn't illegal at that time, yet created a conflict between the public and the law, and examines the justice in the society.
Love Canal was a small town in Niagara Falls, New York, located between two bodies of water: the Bergholtz Creek to the North and the Niagara River to the South. Seems innocent enough right? Wrong. This town was built on top of 21,000 tons of toxic waste (Verhovek). In the early 1890's, William T. Love wanted to build a canal which would connect the Niagara River to Lake Ontario to generate hydroelectric power for his would be city. However, due to a severe drop in investors and laws passed by Congress
As a citizen of the Love Canal, NY it is my duty to advise you the best decisions and living in the Love Canal is not one of them. The Love Canal believes that there toxins buried in the soil could ever be removed. That is a false accusation from the companies, and the assurances. The soils can not be completely cleaned from toxins and chemicals. There are also four other facts as to why and how the love canal is and will never be a safe place for residents. The cost of the house, chemicals
test consists on analyzing if the options perform less harm than the alternatives (Davis, 1999). In other words, this test implies that the benefits need to prevail over the harm, which will minimize the harm and maximizing the benefits. In the Love Canal case, this test failed since it was clear that the well-being of the public was affected due to the birth defects, miscarriages, and health issues that the community exhibited. Similarly, the colleague test consists on asking yourself what your
uk/onthisday/hi/dates/stories/february/2/newsid_2524000/2524997.stm Bucholtz, R. (1991). Corporate responsibility and the good society. Bloomington: Indiana University. Gibbs, L. M. (2003,). History: Love Canal: the Start of a Movement. Retrieved January 27, 2011, from Boston University School of Public Health: http://www.bu.edu/lovecanal/canal/ Stoss, F. W. (1998, gust 2). Love Canal: Reminder of Why We Celebrate Earth Day. Retrieved January 27, 2011, from UC Santa Barbara Library: http://www.library.ucsb.edu/istl/00-spring/article2.html
Margaret Mead, an American anthropologist, once stated, "Never doubt that a small group of thoughtful, committed citizens can change the world. Indeed, it is the only thing that ever has." As humans, we are always observing the world around us, however when we come across something we want to change, it can be a huge undertaking for a single person. The mobilization of resources and people, the arousal of conflict, and the demand for reform are the basic characteristics of a social movement. A social
spread like wildfire. The Love Canal Tragedy that took place in Niagara Falls, NY, is just one example of a public health disaster that affected hundreds of people and even forced them to abandon their homes. What started out as a dream of Mr. William T. Love, a dream of a model city fueled by power generated from digging a canal between the upper and lower Niagara Rivers, eventually turned into a nightmare for so many people (Beck, 2016). In the early 1900's, Mr. William T. Love had a dream of developing

subset: commoncrawl


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Veg Samosa$6
The unbeatable. Fried pastry with a savory filling, spiced potatoes, onions, peas in a cone shape. Two pieces per order.
Chicken Tikka Masala$14
Signature dish. Onion, tomato, creamy cashew sauce cooked with choice of veg or meat with cut onions & bell peppers.
Butter Chicken Masala$14
Rich in flavors. Onion, tomato, garlic, ginger and a exotic spices. Sprinkled with curry leaves, cilantro and coconut
Chicken Curry$14
Rich in flavors. Onion, tomato, garlic, ginger and a exotic spices. Sprinkled with curry leaves, cilantro and coconut
Mango Chicken $15
It's damn good. Chicken curry elevated with the gracious mango goodness. Sweet and spice in one.
Palak Paneer$14
Aloo Gobi$15
Semi-dry mashed potatoes and light seasonings stuffed into the naan bread.
Navratan Korma $15
Lamb Rogan Josh$16
A classic kashmiri dish. Fiery lamb cooked over intense heat with caramelized onions, a splash of vinegar and red curry sauce.
Lamb Vindaloo$14
Chicken Biryani$14
The Party dish. A one pot meal with long grain basmati, veg or meat and aromatic spices slow cooked to perfection (Dum).
Tandoori Chicken$14
The majestic dish. Chicken leg quarts marinated in yogurt and spices, slow cooked in a tandoor (cylindrical clay oven) to perfection and then glazed with caramelized onions and home sauces. Yummm...
Garlic Naan$4
Layer of garlic and cilantro over the naan bread.


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A car stolen in Bradford a week ago has been recovered by police in Huddersfield.
The driver of the silver Nissan Note made off after spotting police.
The vehicle was the a abandoned in a car park and officers said the occupants tried to hide in a nearby shop.
Police have released a picture of the vehicle near the junction of Leeds Road and Thistle Street, Huddersfield.
Two people have been arrested in connection with a recent shoplifting offence.
A spokesperson for West Yorkshire Roads Policing Unit tweeted: "Huddersfield: Vehicle stolen in Bradford a week ago. Vehicle made off on sighting officers. Occupants abandon vehicle in a car park and try to hide in the shop."


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|Fire Marshal issues burn ban for unincorporated areas in King County starting today
|By Administration Raechel Ehlers
|July 27, 2020
With dry conditions in the forecast, King County Fire Marshal Chris Ricketts has issued a Phase 1 burn ban for the unincorporated areas of King County (INCLUDING VASHON) starting today. The ban will remain in effect until further notice.
Even when the Red Flag Warning is lifted, King County's Phase 1 burn ban restrictions will still be in place and apply to all outdoor burning, except for small recreational fires in established fire pits at approved campgrounds or private property with the owner's permission. Recreational fires still pose a risk, so their use shall be limited and respected accordingly. Ricketts says recreational fires must:
Be built in a metal or concrete fire pit, such as those typically found in designated campgrounds; and not be used as debris disposal
For properties located within cities, please contact your local jurisdiction for requirements. This ban remains in effect until further notice.
The King County Fire Marshal reminds residents that it is every individual's responsibility to help prevent fires that destroy lives, property, and our wildland. For more information, visit the Department of Local Services Fire Marshal's website.
|King County Fire Marshal: Burn bans and fireworks
Public Health – Seattle & King County: Hot Weather Tips During a Pandemic
King County Emergency Management: Keep Your Cool This Summer


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July - August 2020
Lucille is a 17 year old Palomino mare. We don't know her history, but TIER found several areas of OLD injuries. She has broken ribs on both sides, a "dent" in her bottom, an indentation where the noseband of a halter goes, muscle atrophy on her forehead. Perhaps she was in a trailer wreck and pulled back? Who knows? The important thing is that this gentle, sweet soul is now safe at TIER.
Like her friend EmmyLou, Lucille is very practical. She would like several storage totes to keep medications and supplies safe and dust-free. A four pack of these tubs is $40.99, but Lucille thinks TIER should probably have eight tubs.
Link to storage totes.
Special Horses, Inc. is a 501(c)(3) organization. It is a GuideStar Platinum Participant and has been a Great Nonprofit since 2015. Since 2009, our mission has been to provide outstanding 501(c)(3) equine rescue organizations with fundraising opportunities, marketing assistance, educational opportunities, grant assistance and community outreach. The organizations we support are dedicated to rescuing, rehabilitating, and rehoming horses in need, and are carefully screened and selected based on their trustworthy reputation, dedication, and excellent service to the animals in their care. Rescuing horses leaves these organizations little time to plan, organize, and execute fundraisers and outreach, and it is the mission of Special Horses to help them help equines in need.


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Laboratoire de Synthèse Organique, CNRS UMR 7652, Ecole Polytechnique, 91128 Palaiseau, France
This article is part of the Thematic Series "Creating complexity" and is dedicated with respect and admiration to Professor K. C. Nicolaou.
Guest Editor: D. Craig
Beilstein J. Org. Chem. 2013, 9, 557–576. doi:10.3762/bjoc.9.61
Received 02 Jan 2013, Accepted 25 Feb 2013, Published 18 Mar 2013
This review article describes briefly some of the radical processes developed in the authors' laboratory as they pertain to the concise assembly of complex molecular scaffolds. The emphasis is placed on the use of nitrogen-centred radicals, on the degenerate addition–transfer of xanthates, especially on its potential for intermolecular carbon–carbon bond formation, and on the generation and capture of radicals through electron transfer processes.
Keywords: amidyls; iminyls; radical allylation; radical vinylation; xanthate transfer
Natural products exhibit an astonishing diversity of molecular architectures and structural complexity. This has spurred the development of numerous synthetic strategies for the rapid assembly of intricate carbon frameworks. In this context, reactions allowing the concomitant or sequential formation of multiple new bonds acquire a special importance [1]. Radicals, in particular, have proved to be especially apt for such a task, and numerous cascade or domino sequences have been described over the past three decades [2-5]. Radicals offer many of the properties desired by synthetic organic chemists, as compared to ionic or organometallic reactions: generally mild and neutral experimental conditions; lower sensitivity to steric hindrance; lower susceptibility to the solvent effects; lesser tendency for rearrangements and β-elimination; and a selectivity that is often complementary to that of ionic or organometallic reactions, making some protection steps superfluous. Radicals are ambiphilic species that can react with both electron-poor and electron-rich substrates, but the rates can differ by several orders of magnitude. The result is a broad spectrum of reactivity that is, paradoxically, often accompanied by a remarkable selectivity.
A major part of our research effort is directed towards the design and development of new radical processes. These include methods for the generation and capture of nitrogen-centred radicals, the degenerative transfer of xanthates and related thiocarbonylthio derivatives, chain processes based on the chemistry of sulfonyl radicals, and electron transfer from metallic nickel to halides and oxime esters. These new reactions can be readily harnessed for the rapid creation of complex molecular structures. The present brief overview aims at giving an idea of the synthetic possibilities.
Nitrogen radicals have received little attention from synthetic organic chemists, in contrast to carbon radicals. Yet their potential for the creation of C–N bonds and for the synthesis of alkaloids is enormous [6]. One possible explanation is the lack, hitherto, of mild yet general methods for the generation of the various types of nitrogen radicals: aminyls, aminiums, iminyls, amidyls, carbamyls, ureidyls, etc.
We discovered some years ago that benzoates of hydroxamic acids, oximes and related derivatives reacted nicely with stannyl radicals to furnish the corresponding nitrogen radicals under mild conditions [7]. These could be readily incorporated into various radical sequences leading to complex nitrogen-containing scaffolds. One illustration is provided by the central transformation in the total synthesis of (–)-dendrobine (4), where the carbamyl radical cyclisation is followed by rupture of the cyclobutane ring [8,9]. This operation, displayed in Scheme 1, starts with benzoate 1 and results in the formation of the carbon–nitrogen bond with the correct stereochemistry and the introduction of the pendant isopropyl group present in the target. The intermediate cyclic carbamate 2 is not isolated but cleaved into aminoalcohol 3 to simplify purification. The conversion of aminoalcohol 3 into (–)-dendrobine (4), hinges on the use of the fabulous Pauson–Khand reaction [10,11] to introduce simultaneously the two adjacent five-membered rings.
Outlined in Scheme 2 is a very short total synthesis of (±)-13-deoxyserratine (11) [12,13]. The first two of the four rings in 11 are again created through the powerful Pauson–Khand reaction starting from trivial enyne 5 and oxidation of the protected alcohol in the side-chain of cyclopentenone 6 directly into carboxylic acid 7 by using Jones' reagent. The second key step, namely the conversion of benzoate 8 into tetracycle 10, involves the concurrent formation of two rings and two adjacent quaternary centres. The chlorine atom in 8 is deliberately introduced in order to direct the second cyclisation towards the 6-endo mode. The chloride in intermediate 9 is now aliphatic and not vinylic as in precursor 8; it is therefore more susceptible to attack by stannyl radicals and the addition of an extra equivalent of tributylstannane ensures its in situ reductive removal. This domino radical cyclisation represents, in fact, a general strategy for the construction of indolizidines and pyrrolizidines, which constitute the core structure of numerous alkaloids. For pyrrolizidines, one needs simply to allow the second cyclisation to proceed in a 5-exo fashion by starting with an un-chlorinated substrate.
The total synthesis of fortucine (15), also hinges on the sequential fashioning of an indolizidine-type skeleton, with the second cyclisation taking place on an aromatic ring (Scheme 3) [14,15]. The formation of the amidyl radical in this case calls for a different precursor and does not involve a stannane reagent. The sequence is triggered by the attack of undecyl radicals on thiosemicarbazone 12. Undecyl radicals arise from the thermal homolysis of lauroyl peroxide and decarboxylation. The lauroyl peroxide must be used in stoichiometric amounts, for it is required to oxidise the intermediate cyclohexadienyl radical 13 into its corresponding cation and thence into intermediate 14 by rapid loss of a proton.
A faster access to complexity is obtained when intermolecular steps are also involved. This increases considerably the convergence of the synthetic scheme. One such instance is pictured in Scheme 4, whereby cyclobutyliminyl radical 17, generated from 16 by a modified Barton decarboxylation [16], undergoes a regioselective scission into secondary radical 18, followed by an initial intermolecular addition to phenyl vinyl sulfone and closure to form the cyclopentane ring in 19, and then by a second intermolecular addition to phenyl vinyl sulfone to furnish radical 20, which finally evolves into the observed product 21 by transfer of the pyridylthiyl group from the starting Barton ester 16. Even though the yield is still on the order of 40% and needs to be optimised, this sequence introduces all the carbons needed for a projected synthesis of (±)-quadrone (22) [17].
This remarkable radical cascade is in fact inspired by an earlier transformation shown in Scheme 5 and starting from simple carboxylic acid derivative 23 [18]. As in the previous sequence, radical 24, generated following the second addition to the vinyl sulfone, is electrophilic in character and does not add further; it simply propagates the chain by reacting with the starting thiohydroxamate 23. The complex bicyclic structure 25 is thus made in just one step. In both of these examples, three C–C bonds and one C–S bond are formed one after the other, resulting in a considerable increase in complexity. Interestingly, and not unexpectedly, the two sulfones in structures 21 and 25 have very different reactivities. For instance, exposure of bis-sulfone 25 to trimethylaluminium causes the regioselective replacement of the terminal sulfone with a methyl group to give compound 26 in good yield. The Barton decarboxylation reaction is an exceptionally powerful method that deserves without doubt a much greater attention from synthetic organic chemists.
A longstanding challenge in organic synthesis has been the intermolecular creation of new carbon–carbon bonds starting with simple unactivated alkenes. The cross-metathesis constitutes at the present time one of the better solutions to this problem [19]. Another solution is the tin-free degenerative radical transfer of xanthates and related derivatives we discovered a quarter of a century ago [20]. The simplified mechanism for the addition to an alkene is depicted in Scheme 6.
The many subtle aspects embodied in the mechanism will not be discussed for lack of space, but the interested reader is directed to a recent review for a more complete description [21]. Experimentally, the procedures are simple and safe, and the reagents are cheap and readily available. In the present context, two properties are especially noteworthy:
(a) The reaction of radical R· with its xanthate precursor 27 to give adduct 28 is fast but degenerate (path A). Radical R· is therefore continuously regenerated and acquires an extended effective lifetime. It can thus be readily captured intra- or intermolecularly, even by unactivated olefinic traps, to give finally adduct 30 (path B). More generally, relatively slow radical processes (additions, cyclisations, fragmentations, etc.) can be accomplished, without need for high dilution or syringe-pump techniques. This property expands considerably the scope by allowing transformations not feasible with other radical methods. The main limitation is that the initial radical R· has to be more stable than adduct radical 29 in order to bias the equilibrium in favour of product 30 and avoid the formation of oligomers by further additions of radical 29 to the alkene. Radicals R· stabilised by electron-withdrawing groups (nitrile, ketones, esters, pyridines, tetrazoles, etc.) are particularly suitable. Benzyl radicals are not reactive enough towards unactivated alkenes; they tend to accumulate in the medium and ultimately dimerise.
(b) The addition product, 30, being itself a xanthate, allows the implementation of a second radical sequence, leading in turn to yet another xanthate. Alternatively, the xanthate group can be exploited as an entry into the extremely rich "ionic" chemistry of sulfur. Thus, a plethora of transformations can be easily marshalled to introduce further diversity and complexity into the structures.
By allowing intermolecular radical additions on unactivated alkenes, the xanthate transfer process opens infinite possibilities for bringing together various functional groups, which can then be made to react together. The functional groups can be present on the xanthate and/or the alkene partners. Over 2000 additions have so far been performed using more than 100 different xanthates. The few examples presented hereafter will hopefully offer a glimpse of the potential for accessing complexity.
The neutral, mild experimental conditions translate into a broad tolerance for sensitive functionality. This aspect is encapsulated in the two addition reactions presented in Scheme 7 [22]. β-Lactam xanthates such as 31 and 33 can be readily added without harm to the fragile azetidinone motif and, if desired, the xanthate group may be reduced off by a number of methods, the mildest perhaps relying on tris(trimethylsilyl)silane as the reducing agent [23]. Its use is illustrated by the synthesis of the β-lactam-sugar conjugate 35, which also highlights the possibility of cleanly removing an oxalyl group from adduct 34 without destruction of the azetidinone [24]. The synthesis of complex compounds such 32 and 35 would be very tedious by more traditional routes.
The possibility of iterating the radical addition allows for a convergent and highly modular assembly of complex scaffolds. The three successive additions outlined in Scheme 8 and leading to 37 illustrate nicely this approach [25]. One xanthate, 36, and three different alkenes are stitched together using the same experimental conditions. The order of the additions is, however, important. One of the requirements, implicit in the general mechanism pictured in Scheme 6, is that the initial radical R· has to be more stable than adduct radical 29, neglecting polar effects in a first approximation (again, [21] may be consulted for a more thorough discussion). A detailed inspection of the various radicals implicated in the sequence in Scheme 8 would reveal that this condition has indeed been respected.
Nevertheless, numerous variations in such sequential radical additions can be readily conceived. This is demonstrated by the key step in the total synthesis of matrine (43), which starts with readily available alkene 38 and xanthate 39, and implies one intermolecular addition followed by two successive cyclisations [26]. Two isomeric tetracyclic compounds 41a and 41b as well as simple addition product 40 are thus obtained in good combined yield (Scheme 9). The latter may be converted into the same mixture of 41a and 41b by further treatment with peroxide. In practice, however, it is more convenient to subject adduct 40 separately to a reductive double cyclisation to give the epimeric mixture of 42a and 42b, by using isopropanol both as the solvent and source of hydrogen atoms. The mixture of 42a and 42b is separated at this stage and the major isomer processed into matrine (43) (the minor isomer has the relative stereochemistry of allo-matrine, also a natural product).
One important property of the xanthate addition–transfer process is that cross-over into a cationic manifold is possible if one of the intermediate radicals can be easily oxidised by the peroxide. The peroxide then acts as both the initiator and the stoichiometric oxidant. This is especially useful in the case of cyclisations onto aromatic or heteroaromatic rings (cf. synthesis of fortucine (15) in Scheme 3 above). The intermediate cyclohexadienyl radicals (analogous to radical 13) cannot propagate the chain but are easily oxidised by the peroxide, which has to be used in stoichiometric amounts. Numerous aromatic derivatives can thus be very easily obtained. In Scheme 10, the synthesis of various tetralones is displayed. The addition of xanthate 44 to two different alkenes furnishes adducts 45 and 48, and these can in turn be cyclised into tetralones 46 and 49, respectively. The former represents a model study for the total synthesis of gilvocarcin M (47), a natural C-glycoside [27]; while the latter illustrates the possibility of constructing a cyclobutane-containing tricyclic motif related to the one found in penitrem D, 50 [28]. The two-step formation of tetralone 53, starting from xanthate 51 and proceeding via adduct 52, underscores the tolerance of the process for the presence of an epoxide and, at least in this case, of a free phenol [29]. This sequence represents an attractive potential route to seco-pseudopteroxazole, 54, and to other congeners in this family.
In many cases, both the intermolecular addition and the ring closure can be performed in the same flask, as shown by the direct synthesis of azaindoline 56 from alkene 55 (Scheme 11) [30]. Azaindoline 56 contains at least four orthogonal sites for diversification, in addition to the obvious possibility of varying the starting xanthate. For instance, a regioselective Sonogashira coupling leading to compound 57 may be performed without affecting the less reactive chlorine substituent. The annelation commencing with xanthate 58 and furnishing indole derivative 59, an advanced intermediate in the formal synthesis of mersicarpine (60), is another illustration [31]. The aromatisation process in this example was incomplete under the usual conditions and required further treatment with manganese dioxide.
The possibility of associating the radical chemistry of xanthates with various ionic reactions represents another powerful strategy for creating complexity from simple starting materials. In this approach, the radical sequence brings together the functional groups necessary for the ionic transformation. One example is the sequence that follows the radical addition of xanthate 61 to an alkene depicted in Scheme 12. Exposure of adduct 62 to the action of potassium carbonate, in a mixture of acetonitrile and tert-butanol under reflux, leads to tricyclic thiochromanone 63 in high yield [32]. This transformation involves attack of the ketone enolate on the thiocarbonyl group of the nearby xanthate, followed by substitution of the fluorine by the sulfide anion thus produced, and loss of a molecule of ethanol. Such, hitherto rare, structures can now be accessed in two easy steps that could in principle be performed in one pot. Variety is readily obtained by merely modifying the alkene or by taking advantage of the presence of the remaining fluorine to introduce different substituents, as shown by the simple formation of trifluoroethoxy derivative 64.
The adducts derived from xanthate 61 can be used in yet another way. Gentle aminolysis of the xanthate frees a thiol, which, under more basic conditions, displaces the ortho-fluorine to afford a benzothiepinone (Scheme 13) [32]. In the particular case of 65a, oxidation to the corresponding sulfone 66 followed by a Mannich reaction with various aldehydes leads to a plethora of complex polycyclic structures 67a–e, which may be viewed as analogues of eptazocine 68 [32]. Oxidation to the sulfone is necessary: when the Mannich reaction of benzothiepinone 65b with formaldehyde was attempted, the reaction resulted in the formation of novel tricyclic sulfonium 69 in modest yield [32].
It is also possible to profit from the ability of xanthates to mediate additions to olefins containing hydroxylamine and hydrazine substituents in order to construct unusual heterocycles [33,34]. One typical illustration is presented in Scheme 14, where unmasking of the hydroxylamine in adduct 70 gives rise to cyclic nitrone 71, which can then be intercepted by a dipolarophile placed in the medium, as shown by the ready formation of bicyclic compound 72 [33].
The use of a phosphonate-containing alkene allows the assembly of numerous polycyclic structures by combining the radical addition of a ketone-bearing xanthate with an intramolecular Horner–Wadsworth–Emmons condensation. This strategy is highlighted in Scheme 15 by the synthesis of bicyclic cyclobutane derivatives 74 and 75 starting from 2-xanthyl cyclobutanone 73 [35]. Thus, depending on the distance between the terminal alkene and the phosphonate, a six- or a seven-membered ring may be fused onto the cyclobutane nucleus.
This combination represents in fact a highly flexible route to polycyclic derivatives, since it is open to numerous variations. For instance, instead of having the phosphonate group attached to the alkene, it can be part of the xanthate component. Such a modification can be used to build the CD ring system found in the highly potent steroid contraceptive desogestrel (79), as outlined in Scheme 16 [36]. Thus, radical addition to alkene 76 furnishes intermediate 77, after deprotection of the second ketone group. Exposure of the latter compound to base results in the formation of bicycle 78 as one diastereomer. While the condensation could in principle take place with either of the two ketones, it occurs in fact selectively with the ketone leading to the xanthate in the equatorial position in order to avoid a 1,3-diaxial interaction with the angular ethyl group. It is worth noting that the xanthate group conveniently occupies the 11-position (steroid numbering) and therefore allows the ready subsequent introduction of various substituents on this important position. In this quite general route to cyclohexenes, the requisite 2-allyl ketones are readily available by alkylation but also, and more importantly, by the exceedingly potent Claisen rearrangement [37], with the attending advantages of stereocontrol and chirality transfer.
Another powerful approach to polycyclic structures is through association with Robinson-type annelations [38]. The synthesis of the precursors also exploits the Claisen rearrangement, as shown by the preparation of enone 81 from allylic alcohol 80 in Scheme 17. By varying the xanthate partner, different substitution patterns and rings may then be introduced. Two examples, 83 and 86, in Scheme 17 illustrate the formation of triquinanes via bicyclic intermediate xanthates 82 and 85. The former involves the addition of a butanoyl radical derived from the corresponding S-butanoyl xanthate, while the latter results from the addition of β-xanthyl ketone 84. The use of an α-xanthyl ketone gives rise ultimately to a fused 6-membered ring, as shown by the formation of tricyclic product 88 from diquinane intermediate 87 [38]. In all of these transformations, the chiral information residing in the starting allylic alcohol 80 is transmitted, through the Claisen rearrangement, to various other centres (the ratios in Scheme 17 and following schemes refer to ratios of diastereoisomers). Very recently, this strategy was applied to a formal synthesis of (±)-hirsutic acid [39].
Access to polycyclic structures can be accomplished by cyclisation of propargyl radicals. Alkynes or allenes can be obtained, depending on the disposition of the internal alkene with respect to the delocalised radical [40,41]. In the sequence displayed in Scheme 18, the addition–cyclisation of a malonyl radical to enyne 89 furnishes allenyl acetate 91 by cyclisation of propargyl radical 90 [41]. Compound 91 readily undergoes reductive dexanthylation and solvolysis into enone 92, and internal Michael addition to give tricyclic structure 93. In this sequence too, the chirality present in the starting material 89 is initially derived from an allylic alcohol by the Claisen rearrangement and is then transmitted to the other centres.
Another powerful reaction that can be associated with the radical chemistry of xanthates is the Birch reduction [42]. The radical process is employed to create the substituted aromatic motif, which is then reduced by the dissolving metal. Scheme 19 contains one such transformation, where the intermolecular radical addition is followed by ring closure to give tetralone 94, which is easily converted into tricyclic derivative 95. An alkylative Birch reduction finally furnishes 96 containing an angular methyl group [43]. This strategy lends itself in principle to numerous modifications, providing access to various ring combinations and substitution patterns.
The facility of introducing polar groups such as ketones and esters through the intermolecular radical-addition step allows the association of the radical ring-closure to aromatic and heteroaromatic derivatives with ionic cyclisation processes. Two such sequences are pictured in Scheme 20. The first combines the radical addition–cyclisation leading to indoline 97 with an intramolecular Friedel–Crafts reaction to afford a tricyclic derivative 98 substituted by a trifluoromethyl group [44]. The second exploits the presence of both a protected primary amine and an easily substitutable chlorine on the pyrimidine ring in 99a,b to afford two interesting tricylic compounds, one of which, 100a, is symmetrical, and the other, 100b, contains a seven-membered ring [45].
One path to complexity is through the use of conjunctive reagents, which can mediate an orthogonal two-directional formation of C–C bonds. In the context of xanthates, two such reagents have been studied. The first is ketophosphonyl xanthate 101, where the intermolecular radical addition on one side of the ketone can be followed by a Horner–Wadsworth–Emmons (HWE) condensation on the other side [46]. In the transformation depicted in Scheme 21, compound 103, obtained by the reductive dexanthylation of adduct 102 derived from 2-allylcyclohexanone, does not undergo an intramolecular HWE condensation to give a cyclooctene derivative upon treatment with sodium hydride. The formation of the cyclooctene ring is not very favourable and cannot compete with the simple aldol process leading to trans-decalin 104. This compound readily undergoes HWE condensation with an external aldehyde, such as benzaldehyde. It is worth noting that β-elimination of water from the resulting product 105 would lead to dienone 106, an interesting substrate for the Nazarov reaction which, in this case, would fuse a cyclopentenone ring on the structure.
The second reagent is chloroacetonyl xanthate 107, which, remarkably, is able to undergo clean radical additions despite the presence of the reactive chloroketone moiety, as demonstrated by its addition to N-allyl-p-chloroacetanilide to give 108 and cyclisation of the latter into indoline 109 [47]. Diverse otherwise inaccessible chloroketones become readily available. Haloketones in general are ideal precursors for the synthesis of numerous heteroaromatic derivatives. For example, Hantzsch condensation of indoline 109 with thionicotinamide furnishes thiazole 110 (Scheme 22). Also interesting is the possibility of substituting the chlorine in 109 with a xanthate salt to form a new xanthate 111 and performing a second radical addition to a different alkene such as vinyl pivalate. The adduct, 112 in this case, is the synthetic equivalent of a 1,4-keto-aldehyde and, in this capacity, can react with ammonia or primary amines, such as cyclopropylamine, to produce the corresponding pyrrole 113 by what may be viewed as a variation of the classical Paal–Knorr synthesis [47,48].
Xanthate 107 is a highly versatile reagent, since it allows the attachment of differing chains on either side of the ketone group by two consecutive intermolecular radical additions to two different alkenes. An application of this property is a simple, yet general route to spiroketals and related derivatives, as shown by the sequence in Scheme 23 [49]. Thus, addition to allyl acetate gives the expected adduct 114, where the chlorine can be readily displaced to provide dixanthate 115. This compound reacts with a second alkene through the xanthate group that leads to the most stable radical, namely the one adjacent to the ketone, to furnish addition product 116. Both xanthates can be reductively removed by treatment with stoichiometric amounts of peroxide in isopropanol as the solvent, and the resulting product 117 saponified and cyclised with acid into spiroketal 118. By choosing a vinyl or a homoallyl ester as the alkene partner, spiroketals of various ring sizes can be easily constructed. Spiroketals 119 and 120 are two such examples. The former was used in the total enantioselective synthesis of (+)-broussonetine G (121) [50]. If one of the alkenes contains a masked aldehyde, a bis-spiroketal such as 122 may be accessed. Furthermore, placing a 1,2- or a 1,3-diol on one of the alkenes would in principle result in the formation of a cyclic ketal. Spiro and cyclic ketals are ubiquitous in pheromones and in marine natural products [51].
The comparatively long effective lifetime of radicals generated under the conditions of the xanthate transfer may be exploited to accomplish various difficult radical transformations. One particularly interesting process is the shifting of an aromatic ring through a radical Smiles rearrangement. In combination with the intermolecular xanthate addition, it becomes possible to rapidly assemble valuable precursors to 3-arylpiperidines. This strategy is illuminated by the synthetic outline in Scheme 24, where the intermediate radical 124 arising from addition to alkene 123 undergoes a 1,2-aryl shift via cyclopropane 125, a process made irreversible by elimination of a methylsulfonyl radical to give ester 126 [52]. Two new C–C bonds are created, and the product now contains two electrophilic centres, a ketone and an unsaturated ester. Treatment with a primary amine or ammonia and in situ reduction of the intermediate imine 127 with sodium cyanoborohydride furnishes arylpiperidine 128 in good overall yield. Ammonia may be replaced with various primary amines, one example being cyclopropylamine, which furnishes piperidine 129 as one stereoisomer. In the case of 1,2-diaminoethane, a further cyclisation is observed leading to bicyclic piperidine 130. All three components involved in this modular approach can be modified to provide a very broad diversity of structures.
Xanthates may be incorporated into radical processes of various kinds. Vinylation and allylation reactions are particularly appealing, in view of the importance of such transformations in organic synthesis. A number of methods were developed to this end, with perhaps the most versatile relying on the chemistry of sulfones [53]. Aliphatic sulfonyl radicals are able to extrude sulfur dioxide, and the resulting carbon-centred radicals may be used in numerous ways. In particular, they can serve as chain-propagating agents for the xanthate-transfer process. An example is provided in Scheme 25 illustrating a rapid, convergent access to cyclopentanols and to functional allenes. Thus, the xanthate group in adduct 131, derived from the radical addition to vinyl trimethylsilane, can be replaced by a dichlorovinyl motif through a second radical reaction with dichlorovinyl ethylsulfone (132) [54]. The ethylsulfonyl radical created in the addition–elimination process of intermediate radical 133 fragments to liberate sulfur dioxide and an ethyl radical that is capable of propagating the chain. The resulting product 134 possesses an interesting combination of functional groups. Upon treatment with magnesium turnings in methanol, this compound is converted into cyclopentanol 135 by capture of the intermediate ketyl radical by the dichlorovinyl group [55]. Alternatively, protection of the ketone and application of the Corey–Fuchs reaction followed by quenching of the acetylide with cyclohexanone furnishes propargyl silane 136, a compound that is cleanly transformed into allene 137 upon exposure to tetrabutylammonium fluoride [54]. This approach represents perhaps the most versatile route to functional propargyl silanes. Indeed, a broad diversity of such structures becomes accessible by simply varying the starting xanthate and/or the ketone (or aldehyde) partner.
Allylations can be accomplished by applying the same concept, as shown by the sequence in Scheme 26 [56]. Again, complexity may be attained by combining the normal addition–transfer of a xanthate to an alkene with the allylation process to give fairly elaborate compounds, such as 140 obtained by reaction of adduct 138 with sulfone 139 [56]. It is interesting to note that both the vinylation and the allylation reactions are applicable to aliphatic iodides, as illustrated by the second transformation in Scheme 26 starting with iodide 141 and leading to dichlorovinyl lactone 142 [57]. It is interesting to note that while sp2–sp2 couplings are readily accomplished starting with vinylic or aromatic iodides using a variety of transition–metal catalysts, especially palladium-based complexes, sp3–sp2 couplings remain relatively rare, especially with secondary and tertiary aliphatic iodides. The present radical procedure therefore complements organometallic methods since it is most efficient with secondary and tertiary iodides, because the corresponding carbon radical is easiest to generate.
Various radical allylating agents can effect the allylation of xanthates. These include substituted allyl diphenylphosphine oxides [58], vinyl epoxides [59], and allyl trimethylsilanes [60]. In the last case it is a two-step procedure. Two examples of the use of a vinyl epoxide as an allylating agent are displayed in Scheme 27 [59]. The first corresponds to the allylation of cyclobutyl xanthate 143 with vinyl epoxide 144 to yield compound 145, while the second involves an addition–fragmentation of xanthate 146 on β-pinene to give xanthate 147, which is then subjected to the allylation procedure with the simplest vinyl epoxide to furnish derivative 148. It is interesting to note that the carbon–carbon bond formation takes place in ketoester xanthate 146 on the carbon bearing the least acidic hydrogens. Triethylborane, through its autoxidation, serves to initiate the process; it also quenches the intermediate alkoxy radical, liberating concomitantly an ethyl radical to propagate the chain.
Except in the cleavage of epoxides, homolytic rupture of carbon–oxygen bonds is generally a difficult process. Radicals can thus be generated next to alcohols or esters without fear of β-elimination. This constitutes a tremendous synthetic asset and explains the popularity and importance of radical-based methods for the manipulation and modification of oxygen-rich compounds such as carbohydrates and cyclitols. It is, however, possible to transform an alcohol into a leaving group in the radical sense by converting it into a fluoropyridineoxy derivative by reaction of the alkoxide anion with inexpensive 2,6-difluoropyridine [61-65]. In this manner, any allylic alcohol becomes a potential radical allylating agent. This has proved to be a powerful route to complex alkenes, as indicated by the two examples in Scheme 28. The first represents a one-step synthesis of a steroid C-glycoside 149 [66], while the second illustrates a modular approach where the formation of alkene 152 is associated with the initial addition–transfer of cortisone derived xanthate 150 to vinyl acetate to provide intermediate xanthate 151 [65]. In this manner, a highly functionalised steroid containing a fluoro-substituted alkenyl side chain can be readily assembled. Both steroid products 149 and 152 would be exceedingly tedious to make by more conventional approaches.
The ability to generate an alkene by the homolytic cleavage of a C–O bond is a recent development that nevertheless holds much promise. It is open to numerous variations, in particular for the synthesis of highly functionalised ketones [64] and for the stereoselective formation of di- and tri-substituted alkenes [63].
A final topic in this brief overview concerns the use of electron transfer from metallic nickel as a means for producing and capturing radicals from selected substrates. The underlying principle is quite simple. It hinges on the observation that the intermediate radical in the dissolving metal reduction of α-halocarbonyl derivatives could be captured by an internal alkene, if the second electron transfer is slow enough. For instance, in the dechlorination of trichloroacetamide 153 with the popular zinc/acetic acid combination, the second electron transfer leading to anion 155 is too rapid to allow interception of intermediate radical 154. No cyclisation is thus observed under these conditions, which initially afford monodechlorinated product 156 and ultimately the completely reduced material 157 (Scheme 29). In contrast, replacing zinc with plain nickel powder and diminishing the acidity of the medium by addition of a cosolvent allows the cyclisation to proceed. The resulting secondary radical 158 is not sufficiently electrophilic in character to be reduced by the metal and can be trapped by various external reagents, as exemplified by the rich array of lactams 159a–f [67]. In the case of ketoester 159c, the reaction was carried out at room temperature [68]. The formation of unsaturated lactam 159f is particularly interesting, since it involves the use of a mild oxidant (cupric acetate) in a reducing medium [69]. Another remarkable feature is that the nickel/acetic acid reducing system is capable of cleanly distinguishing between the starting trichloroacetamide and the dichlorolactam product. They have relatively close reduction potentials, yet the latter is reduced much more slowly under these conditions.
A further synthetically valuable observation is the behaviour of ene-trichloroacetamides such as 160 (Scheme 30) [70]. In this system, the intermediate radical 161 undergoes a 5-endo cyclisation into the easily oxidised tertiary radical 162, which is then logically converted into cationic species 163 by electron transfer to the starting trichloroacetamide 160. Loss of a proton finally provides unsaturated dichlorolactam 164. This compound cannot be isolated because the chlorines are now allylic and therefore easier to reduce off than those of the starting material. Thus, a second chlorine atom is lost through reduction and the last is simply eliminated as chloride to give diene 165 as the final product. In the presence of cupric acetate additive, which somehow slows down the reduction, the elimination of chloride is faster than reduction, and it is chlorodiene 166 that is ultimately formed [70]. Since HCl is formally produced in these transformations, the addition of sodium acetate to buffer the medium is often beneficial.
The easy access to unsaturated lactams such as 165 and 166 may be exploited to construct complex structures by subsequent application of radical, ionic, or organometallic transformations. This is illustrated by the short, six-step total synthesis of (±)-3-demethoxy-erythratidinone (170) displayed in Scheme 31 [71]. In this approach, trichloroacetenamide 167, trivially obtained in two steps from monoprotected cyclohexanedione, is subjected to the cyclisation sequence to give diene 168, which smoothly undergoes an intramolecular Friedel–Crafts reaction to generate the last ring in intermediate 169. Finally, reduction of the lactam and unmasking of the ketone causes the migration of the olefin to complete the synthesis of the target structure 170.
The generation of radicals using nickel powder in combination with acetic acid can be extended to the production of iminyls by reduction of oxime esters [72,73]. This variant allows an easy access to pyrrolenines as underscored by the synthesis of complex structure 173 from thebain-derived oxime pivalate 171 via iminyl radical 172 (Scheme 32) [73]. In this transformation, the solvent, 2-propanol, acts as the final hydrogen atom donor to quench the carbon radical formed upon cyclisation of the iminyl.
The preceding examples showcase some of the possibilities for creating complexity by using radical processes we have developed over the years. Our research is curiosity driven, guided by a search for novelty and a thirst for understanding reaction mechanisms. Constructing complex molecular architectures is only incidental to our work, mostly a consequence of our exploration of the scope and limitations of our methods. The degenerative radical addition–transfer of xanthates is by far the most powerful radical chemistry that we have been able to discover, for it allows efficient intermolecular carbon–carbon bond formation starting with unactivated alkenes under very mild experimental conditions. Various functional groups can therefore be brought together and made to react in an infinite number of ways. Because of its convergence and tolerance, the xanthate technology offers numerous possibilities for the rapid assembly of well-decorated, intricate carbon frameworks. Much work has been done, but much more remains to be done in this never-ending quest, which will hopefully continue to take us to unexpected venues.
We are extremely grateful to our collaborators and students, whose names appear in the references, and who made this chemistry possible through their skill, dedication, and enthusiasm. We also thank the following organisations and companies that have provided financial support over the years: École Polytechnique, CNRS, MNRT, DGA, MNRT, ANR, the Alfred Kastler Foundation, CONACyT (Mexico), MECyD (Spain), the Royal Commission for the Exhibition of 1851, Rhodia, Scynexis, and Sanofi-Aventis.
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© 2013 Quiclet-Sire and Zard; licensee Beilstein-Institut.
This is an Open Access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (http://www.beilstein-journals.org/bjoc)


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Jan Žižka partisan brigadejan žižka partisan brigade 2017, jan žižka partisan brigade 2016
The 1st Czechoslovak Partisan Brigade of Jan Žižka Czech: 1 československá partizánská brigáda Jana Žižky or Partyzánská brigáda Jana Žižky z Trocnova, initially known as Ušiak-Murzin Unit, was the largest partisan unit in the Protectorate of Bohemia and Moravia modern day Czech Republic during the German occupation of Czechoslovakia After its core membership of Soviet-trained paratroopers were dropped into Slovakia in August 1944, the brigade crossed into Moravia and began operations in earnest at the end of 1944 Its focus was guerrilla warfare, especially sabotage and intelligence gathering
- 1 Background
- 11 German occupation
- 12 Military situation
- 2 History
- 21 Formation of the unit
- 22 Transfer to Moravia
- 23 Consolidation at Čertův Mlýn
- 24 German countermeasures
- 241 Gestapo ruse
- 242 Operation Grouse
- 25 Reorganization
- 3 Operations
- 31 Sabotage
- 32 Intelligence
- 33 Countermeasures
- 4 Legacy
- 5 Notable members
- 6 References
- 61 Notes
- 62 Citations
- 63 Bibliography
German occupationSee also: Munich Agreement and German occupation of Czechoslovakia The Protectorate, Slovakia, and neighboring countries
In 1938, German Chancellor Adolf Hitler announced his intentions to annex the Sudetenland, a region of Czechoslovakia with a high ethnic German population As the previous appeasement of Hitler had shown, the governments of both France and Britain were intent on avoiding war[2] British Prime Minister Neville Chamberlain and other Western political leaders negotiated with German Chancellor Adolf Hitler and ultimately acquiesced to his demands at the Munich Agreement, in exchange for guarantees from Nazi Germany that no additional lands would be annexed No Czechoslovak representatives were present at the negotiations[3] Five months later, when the Slovak Diet declared the independence of Slovakia, Hitler summoned Czechoslovak President Emil Hácha to Berlin and forced him to accept the German occupation of the Czech rump state and its re-organisation into the German-dominated Protectorate of Bohemia and Moravia[4] Germany promptly invaded and occupied the remaining Czech territories Although France had a defensive alliance with Czechoslovakia, neither Paris nor London intervened militarily[5]
The Nazis considered many Czechs to be ethnically Aryan, and therefore suitable for Germanisation[6] As a consequence, the German occupation was less harsh than in other Slavic nations For example, food rations in the Protectorate of Bohemia and Moravia were almost identical to those in Germany[7] The occupation influenced the daily life of ordinary Czechs by the militarisation of the economy, the elimination of political rights, and transportation to Germany for forced labour[8] More than 20,000 Czechs were executed, and thousands more were deported to concentration camps[9] While the general violence of the occupation was less severe than in Eastern Europe,[10] it nevertheless caused many Czech people to hate the Germans living within the Protectorate, and support partisan groups[11]
Military situationSee also: Bandit fighting and Czech resistance
Although there was wide popular support for the resistance, in other ways the Protectorate was ill-suited to partisan activity There were very few guns, despite the relatively liberal firearms policies in place prior to the occupation[12] The Protectorate was highly urbanized, which made the establishment of partisan field camps in woods or mountains impractical, and the excellent transport and communications infrastructure was at the disposal of the Nazi security apparatus Also, the ethnic German minority tended to cooperate with the occupiers and some local Germans joined the security forces, which benefited from their fluency in Czech and knowledge of the local geography[12]Hostýn-Vsetín Mountains, base of the Green Cadre
The Nazi administration brought in Reinhard Heydrich as Deputy Protector of Bohemia and Moravia in order to enforce policy more harshly[13] His brutality led to the Allies ordering his assassination in May 1942[14] In the violent crackdown that followed, known in Czech as the Heydrichiáda [cs], more than a thousand Czechs were murdered, including the entire village of Lidice[15] Some former members of the resistance evaded arrest by fleeing into the Moravian mountains and forming partisan groups[16] The first documented partisan group was the Green Cadre Czech: Zelený kádr, active in the Hostýn-Vsetín Mountains along the Czech-Slovak border from early 1942[17] There were also urban resistance groups, such as the White Lioness Czech: Bílá lvice active in the areas of Silesia around Frýdek-Místek and Ostrava[18][19] Such partisan groups depended on the support of the local population and acted by cutting power lines and sabotaging railways[20] Beginning in April 1944, several paratrooper groups trained in Britain were dropped in Moravia in order to gather intelligence[21][a] However, according to historian Detlef Brandes, the emergence of the Žižka brigade was the beginning of effective guerilla resistance in the Protectorate[26]
Formation of the unitSee also: Slovak National Uprising
At the end of 1943, Czechoslovak Communist politicians asked the Soviet government to organize a partisan movement in the Protectorate and Slovakia Partisan units for deployment in Czechoslovakia received training in Sviatoshyn, a suburb of Kiev To support advancing Soviet troops, paratroopers were deployed in advance, initially in Carpathian Ruthenia, then in Slovakia and finally also in Moravia[27]
The partisan group that would become known as the Jan Žižka brigade was formed during training in Sviatoshyn Most of its initial twenty-one members, including the commander, Lieutenant Ján Ušiak [cs; sk], were ethnic Slovaks, in accordance with the initial plans to deploy in Slovakia Before the training at Sviatoshyn, some of them had fought as partisans in Belarus or in the Crimea/Odessa region The unit also included Hungarian defectors and seven Soviets, including Captain Dajan Bajanovič Murzin [cs], second-in-command[28]
The "Ušiak-Murzin Unit" parachuted near Sklabiňa, Slovakia in two groups, on the night of 21-22 August 1944 and the night of 30-31 August[29] The day before the first group arrived, a local partisan group which controlled the area had publicly announced the restoration of the Czechoslovak state[30] The original orders had been for the unit to cross the Fatra mountain range and begin operations in northwest Slovakia However, the plans were disrupted by the Slovak National Uprising, which began 29 August Initially, the unit conducted reconnaissance on a German counter-offensive, but soon Ušiak received orders to redeploy to Moravia, and on 6 September they began to move north The Ušiak-Murzin Unit was joined by many Czech fugitives who wanted to fight on their own territory[31] Other recruits were former Slovak Army soldiers[32]
Transfer to MoraviaŠtiavnikVelké KarloviceSklabiňa Movement through 10 October
Although the partisans had intended to reach the border undetected, there were two skirmishes before the unit reached Štiavnik, a Slovak town near the border Since the Štiavnik police and other Slovak forces in the area had defected to join the Slovak National Uprising, the unit, now grown to 150 members, established itself around Štiavnik, controlling a small area to the rear of the German forces[32] In Štiavnik more troops joined the unit, mostly Czechs crossing the border from the Protectorate in order to join the Uprising, but they also included escaped Soviet prisoners of war who had fled from camps as far away as Saxony and crossed Bohemia and Moravia with the help of the local population The unit was formally named after Jan Žižka, the 15th century leader of the Hussite army, whose fight for religious freedom and use of innovative military techniques had made him a Czech national hero[33]View of Štiavnik from Doktorovec hill
In order to stem the flow of Czechs joining the Slovak National Uprising, the Germans closed the border and made unauthorized crossing punishable by death on 16 September[34] Attempts to cross the border as a unit were made on the nights of 21-22 and 24-25 September near Velké Karlovice As both attempts failed after skirmishes with German border guards, Murzin crossed the border with a smaller group of 60 partisans on the night of 28-29 September[35] Some 300 partisans remained in Slovakia, their numbers daily augmented by newcomers[36] In early October, the border was reinforced by about 300 SS military policemen, making it more difficult for the Žižka partisans to cross back into Moravia[37] On 10 October, the Germans attacked Štiavnik Fighting lasted for about three days with partisan losses estimated at 200[clarification needed] around Štiavnik and in skirmishes with border guards while attempting to cross into Moravia[38] Only 130-140 guerrillas managed to cross the border;[39] those left behind included twelve of the fourteen Soviet-trained Slovaks[40]
Consolidation at Čertův MlýnVsetínTrojačkaMagurka / Čertův Mlýn Operations in October 1944
In Moravia, the unit settled in a hunting lodge on the slopes of Magurka Mountain [cs][35][41] and made contact with the British-trained Wolfram partisan group[b] Concerned that an attack by American bombers on 14 October had drawn unwanted attention from German security forces, the Murzin partisans took refuge in the Wolfram group's base at Trojačka [cs; sk; sv][40][41][43] Because the Wolfram group was expecting an airdrop of supplies from Britain, twenty-one partisans were transferred from the Murzin group to Wolfram In exchange, Murzin received a significant amount of money necessary to fund his operations[44]Woods around Trojačka
One of those transferred was Stanislav Kotačka [cs],[45] a petty thief who had joined the partisans to avoid detention in a concentration camp[46] After murdering a Wolfram partisan,[47] he turned himself in and offered to inform on the partisans in exchange for erasing his criminal record[41][48] At 4:30 on 23 October, he led 300 German soldiers to the base, but the partisans managed to escape[49][50] While German security forces burned buildings and terrorized civilians in the area around Trojačka, the Žižka partisans separated from the Wolfram group and established a new, more permanent base at Čertův Mlýn [cs; pl][c] They benefited from supplies and information provided by friendly Czech civilians, some of them members of Obrana Národa[51][52]
Two groups were sent further southwest, under the command of Ivan Petrovič Stěpanov and Viktor Ševcov-Grekovskij[53] They made contact with other groups already established in and around Vsetín[54][d] The groups gathered clothing and provisions for the winter and raided police stations sometimes in cooperation with local Czech policemen for firearms and ammunition[56] By the end of October, the unit had grown to over 200 men and women, divided into four sub-groups: one guarded the base while the other three operated in the surrounding area[57]
German countermeasures
Gestapo ruse
The Gestapo attempted to lure the unit's leaders into a meeting with agents who presented themselves as leaders of communist resistance groups Ušiak was unaware that almost all resistance organizations had been infiltrated by the Gestapo and their members caught and executed Therefore, he agreed to a meeting on 2 November, in a location not far from the base Unbeknownst to the Gestapo, however, anti-partisan army units were also deployed in the area and by chance turned up at the meeting, spoiling the Gestapo's plans[58][59] Both Ušiak and Murzin were wounded in the ensuing gunfight, and fled in different directions Ušiak was hidden by civilians in Čeladná, but was soon tracked down and committed suicide to avoid capture[60] Murzin was hidden for three weeks in a forest dugout, but the partisans did not know his whereabouts[61][62] Meanwhile, Germans captured another partisan who revealed names of civilians who had aided the partisans[59][63] In a raid on the base the next day, four partisans were killed and two others captured[64]@media all and min-width:720px}
|Operation Grouse
|Part of German occupation of Czechoslovakia
|RožnovFrenštátČeladnáStaré HamryChata Bečvice
German cordon area[65]
|Nazi Germany
|Commanders and leaders
|Josef Otisk [cs]
|Units involved
Jan Žižka partisan brigade
Wolfram group [cs]
|~ 200
|Casualties and losses
|6 killed, 3 wounded[67]
|8 killed, 4 captured[67]
|13-40 civilian suspects were arrested and executed[67]
On 3 November, Higher SS and Police Leader Karl Hermann Frank ordered the summary executions of suspected partisans along with those suspected of helping them The bodies of executed suspects were to be hanged in public for 48 hours[68][69] A wave of arrests and executions decimated the civilian supporters of the partisans[70] Although the Czech police forces often supported the partisans,[71] they undermined the public approval for them by stealing from Czechs,[72] and some civilians did inform on the partisans[73] Due to the increasing partisan activity in the area, the Germans posted guards at railway bridges to prevent sabotage[74]
Operation Grouse
Operation Grouse Czech: Tetřev, German: Auerhuhn started on the morning of 16 November, when the Germans sealed off a cordon area defined by the towns of Rožnov, Frenštát, Čeladná, Staré Hamry, and Chata Bečvice[65] The 55-kilometer cordon was carefully monitored and no one was allowed entry or exit; a system of passwords was employed to prevent guerrillas from impersonating German soldiers[75] The commander, Generalleutnant Hans Windeck [de], aimed to flush the partisans out of the dense forests on the east of the cordon area into the more open areas to the west,[76] and there decisively destroy both Wolfram and the Žižka partisans[77] The Germans committed some 13,000 soldiers and police to the operation[66][77][e] However, due in part to inclement weather, the cordon was not as impervious as the Germans intended, and the local population helped partisans escape at night[79] Poor coordination between the Wehrmacht and police forces hampered the effectiveness of the operation[80] Georg Attenberger, an SS officer involved in the operation, also blamed the insufficient training of the Wehrmacht units[81] and the laziness of the police[82]
For their extensive manpower deployment, the Germans had little to show: only eight partisans killed and between 13 and 40 suspected civilian supporters captured and executed, at the cost of six German soldiers killed and three wounded[67] After the operation, no guerrilla activity was reported in the cordon area, but increased outside of it[83] The Žižka brigade had lost its base, provisions, and radio communication with the Red Army[84] The German show of force discouraged the civilian population from providing food and intelligence to the partisans[85][86] To make matters even worse, the fate of the unit's commanders remained unknown It took another two weeks to transport Murzin, the surviving commander, to the partisans' new operational area in the Hostýn-Vsetín Mountains[61]
Stěpanov's and Ševcov-Grekovskij's groups had established themselves outside the area blockaded by Operation Grouse[87] After being transported to the new base, Murzin assumed command The unit was restructured and its tactical approach transformed It was divided into smaller groups which were spread over a wider area, and avoided staying in one place for too long[88] Most command positions were taken by escaped Soviet POWs, who had more military experience By the end of the war, the command structure was largely decentralized and the brigade was operating in a large area in eastern and central Moravia[89]
With brigade membership rising, Murzin decided to restrict the number of partisans accepted into the forest units due to the limited supply of food and weapons[f] Preference was given to escaped POWs and to Czech resistance members who had been exposed and were evading arrest Those turned away were instructed to start their own partisan units in the urban areas Some members lived a double life, joining the partisans only for night raids[90]
SabotageSpecific aspects of waging partisan warfare in Moravia involved the following factors:
- a dense network of military garrisons
- military control and protection of military and industrial premises, roads, railway stations, bridges and administrative institutions
- a diversified Gestapo network supported by spies in towns, settlements and villages
- special penal units of SS, Schutzpolizei, and field gendarmes in the mountains and woods, in areas known to contain partisan bases and battalions
The extent of brigade operations was constrained by availability of armaments Following Operation Grouse, the brigade was scattered and had lost most of their ammunition and explosives[91] Therefore, in December the partisans were forced to focus on consolidation and acquiring weapons, with offensive operations gradually increasing from January[92] During the early months of 1945, many retreating German and Hungarian units passed through or were stationed in the brigade's operational area This led to the acquisition of a large number of guns from raids; demoralized Hungarian soldiers would often trade their weapons for food or drink[93]
Avoiding direct encounters with larger German units, the partisans sabotaged railways, bridges, telecommunications and factory power-lines[92] The brigade's most important operations relied on the use of improvised explosive devices Most of the explosives were either seized from the German forces or from civilians For example, 600 kg 1,300 lb originally intended for a quarry was stolen in January The explosives experts were mostly Czech civilians who joined the brigade[94] By March 1945 the brigade was conducting raids on daily basis[95] One of its most celebrated operations was the capture of Generalleutnant Dietrich von Müller, the commanding officer of Germany's 16th Panzer Division, on 19 April[96]Memorial to fallen members of the brigade's group Olga, which captured Müller
When the front-line reached the brigade's operational area on 26 April, the partisans took part in front-line operations Many then joined the army units in their campaigning further west, being used mostly as armed intelligence personnel[97]
Apart from disruption of the German rear, the brigade's other strategic objective was gathering intelligence Effectiveness of intelligence support to the Soviet war effort was much reduced with the loss of radio communication on 12 November By the end of December, the brigade's staff were back in contact with the Red Army, using the radio of the Luč intelligence unit which had recently been parachuted to the area However, the communications disruption also necessitated a period of confidence rebuilding; during the weeks of radio silence the Soviet commanders had believed the unit lost[98] By then, a rivalry had developed between the brigade and 1st Ukrainian Front's intelligence officers[99]
The partisans gathered information on the positions, armaments and strength of German units, the locations of armories and warehouses, the position of fortifications, and status reports concerning airfields, movements and transportation of German units Information was also provided on ethnic Germans, Czech collaborators and informers, as well as on the fighting operations of the brigade itself and on its civilian supporters[100] Much important intelligence came from Government Army policemen, some of whom actively assisted the partisans by causing diversions for raids or fighting alongside the partisans However, the brigade's most valuable intelligence source was the commander of the German barracks in Holešov, Major Josef Hübner Hübner used his personal driver, anti-fascist Hans Kocher, to pass information on planned raids and the uncovering of resistance members[101]
The German occupation forces redeployed a Waffen-SS platoon, the 31st Special Operations Group, along with their 20th SS Police Regiment, to Moravia The 31st Special Operations Group was experienced in anti-partisan warfare from previous experience in Yugoslavia, and was also known for its brutality towards Czech civilians[102] German forces murdered civilians suspected of supporting the partisans,[95] sometimes beating pregnant women to death[103] as well as burning suspects alive[104] German counter-intelligence also employed a fake partisan unit consisting of 16 Russian Liberation Army soldiers led by an ethnic German bilingual in Czech,[105] but failed to infiltrate the brigade when the ruse was discovered[106]
The brigade was demobilized on 26 May 1945, having been deployed in the days immediately after the war as a security force searching for German soldiers hiding in the Moravian mountains and forests[107] According to Murzin's post-war report, the brigade consisted of 1,232 people on 5 May 1945[1][g] 1,533 persons had been members, of which 304 were killed and 208 wounded[108] A significant number of partisans and many who aided them were women[109] 1,126 members were decorated by the Czechoslovak government, more than any other partisan unit[108][h]
The brigade has a controversial legacy in Moravia, partly due to its Soviet affiliation;[110] the Communist regime was accused of glorifying Soviet partisans including the Jan Žižka brigade[109] Partisans were frequently described as drunkards, adventurers, and bandits, who were more of a threat than the German occupiers[110][i] The partisans did steal from locals who were unwilling to feed them,[72] executed German prisoners, and conducted summary executions of civilians suspected of collaboration, some of whom turned out to be innocent[109]
Notable members
- Alexander Dubček joined the brigade in August 1944[111]
- Max Hrdliczka, shareholder of Impregna AG in Bystrice pod Hostynem supported Jan Ziska financially via his bookkeeper Oldrich Dolak, Karel Bubenicek from Impregna AG, production manager, was active member of Jan Ziska, source: Karel Bubenicek; Partyzani na domaci Front, 1982, Lipnik n Bec
- ^ In 1944, the British dropped the following groups into Moravia:
- April: Operation Carbon [cs] and Operation Clay[22]
- May: Operation Spelter [cs][23]
- July: Operation Potash [cs][22]
- September: Operation Wolfram [cs][24]
- December: Operation Tungsten cs[25]
- ^ The Wolfram group's purpose, unlike the other British-supported groups, was to incite a Czechoslovak guerrilla movement among the local population[42]
- ^ A mountain 04 km from Magurka
- ^ Including Pro vlast,[55] the Štramberk partisans,[53] Clay,[55] the Lipták Group[56] and Josef Sousedík's organization[55]
- ^ Forces committed included units of the Allgemeine SS, Gestapo, and Kripo, as well as regular Wehrmacht troops[78]
- ^ Most guns were taken from German security forces during raids In February 1945, eleven Belgian members of Technische Nothilfe, entrusted with the protection of an arms factory in Jablunkov, deserted and joined the brigade, bringing with them a significant stockpile of arms and ammunition[90]
- ^ 927 Czechs and Slovaks, 257 Soviet citizens, and 48 partisans of other nationalities, including German anti-fascists, an Austrian deserter, Hungarians, and Romanians More than 20 nationalities were represented[1]
- ^ 203 partisans of the Jan Kozina Brigade and 155 partisans of the Jan Hus Brigade [cs] were decorated[108]
- ^ In order to counter such perceptions, surviving members commissioned a history of the brigade by Marie Hrošová[110]
- ^ a b c Hrošová 2012, pp 156-157
- ^ Noakes & Pridham 2010, p 102
- ^ Bryant 2007, p 24
- ^ Noakes & Pridham 2010, p 119
- ^ Bryant 2007, p 28
- ^ Bryant 2007, p 126
- ^ Staff, US Congress 1945, p 908
- ^ Bartošek 1965, p 96
- ^ Ėrlikhman 2004, p 54
- ^ Bryant 2007, p 62
- ^ Frommer 2005, p 42
- ^ a b Hrošová 2012, p 17
- ^ Williams 2003, p 82
- ^ Burian 2002, p 31
- ^ Burian 2002, p 90
- ^ Suchánková 2013, pp 5, 18
- ^ Hrošová 2012, p 16
- ^ Hrošová 2012, p 18
- ^ Suchánková 2013, p 18
- ^ Suchánková 2013, pp 18-19
- ^ Suchánková 2013, p 19
- ^ a b Ziková 2011, pp 19-20
- ^ Ziková 2011, pp 19-21
- ^ Ziková 2011, pp 19, 26
- ^ Ziková 2011, p 19
- ^ Brandes 1999, p 425
- ^ Hrošová 2012, pp 20-23
- ^ Hrošová 2012, p 24
- ^ Suchánková 2013, p 21
- ^ Hrošová 2012, pp 30-34
- ^ Hrošová 2012, pp 35-36
- ^ a b Hrošová 2012, pp 38-46
- ^ Hrošová 2012, pp 46-50
- ^ Suchánková 2013, p 15
- ^ a b Ziková 2011, p 45
- ^ Hrošová 2012, p 58
- ^ Suchánková 2013, p 16
- ^ Přikryl 1976, p 99
- ^ Ziková 2011, p 46
- ^ a b Černota 1990, p 61
- ^ a b c Suchánková 2013, p 23
- ^ Suchánková 2013, p 20
- ^ Ziková 2011, p 47
- ^ Ziková 2011, pp 48-49
- ^ Ziková 2011, p 48
- ^ Ziková 2011, p 44
- ^ Ziková 2011, p 50
- ^ Ziková 2011, p 56
- ^ Ziková 2011, p 58
- ^ Suchánková 2013, p 24
- ^ Hrošová 2012, p 74
- ^ Suchánková 2013, pp 23-24
- ^ a b Hrošová 2012, p 79
- ^ Hrošová 2012, pp 79, 81, 82
- ^ a b c Hrošová 2012, p 81
- ^ a b Hrošová 2012, p 82
- ^ Hrošová 2012, p 83
- ^ Hrošová 2012, p 88
- ^ a b Suchánková 2013, p 27
- ^ Suchánková 2013, p 28
- ^ a b Hrošová 2012, p 108
- ^ Suchánková 2013, pp 28-30
- ^ Hrošová 2012, p 92
- ^ Suchánková 2013, p 31
- ^ a b Suchánková 2013, p 49
- ^ a b Hrošová 2012, pp 96-99
- ^ a b c d Hrošová 2012, p 100
- ^ Hrošová 2012, p 93
- ^ Suchánková 2013, p 33
- ^ Suchánková 2013, pp 34-37
- ^ Suchánková 2013, p 38
- ^ a b Suchánková 2013, pp 38, 42
- ^ Suchánková 2013, pp 38-41
- ^ Suchánková 2013, p 42
- ^ Suchánková 2013, p 50
- ^ Suchánková 2013, p 52
- ^ a b Ziková 2011, p 7
- ^ Suchánková 2013, p 51
- ^ Suchánková 2013, pp 68-69
- ^ Suchánková 2013, p 69
- ^ Suchánková 2013, p 72
- ^ Suchánková 2013, p 74
- ^ Suchánková 2013, pp 76-77
- ^ Suchánková 2013, p 77
- ^ Suchánková 2013, p 76
- ^ Hrošová 2012, p 105
- ^ Hrošová 2012, p 107
- ^ a b Hrošová 2012, p 117
- ^ Hrošová 2012, p 156
- ^ a b Hrošová 2012, p 133
- ^ Hrošová 2012, p 164
- ^ a b Hrošová 2012, pp 171, 176
- ^ Hrošová 2012, pp 180, 196
- ^ Hrošová 2012, pp 176-177
- ^ a b Hrošová 2012, p 210
- ^ Hrošová 2012, p 209
- ^ Hrošová 2012, p 217
- ^ Hrošová 2012, pp 230-231
- ^ Hrošová 2012, p 257
- ^ Hrošová 2012, p 255
- ^ Hrošová 2012, p 260-261
- ^ Hrošová 2012, pp 165-166
- ^ Hrošová 2012, pp 195, 200
- ^ Hrošová 2012, p 187
- ^ Hrošová 2012, p 191
- ^ Hrošová 2012, p 192
- ^ Hrošová 2012, p 126
- ^ a b c Hrošová 2012, p 158
- ^ a b c Gazdík 2008
- ^ a b c Gazdík 2013 sfn error: no target: CITEREFGazdík2013 help
- ^ Kirschbaum 2016, p 239
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