{'fraction_non_alphanumeric': 0.021669341894060994, 'fraction_numerical': 0.0056179775280898875, 'mean_word_length': 6.00561797752809, 'pattern_counts': {'":': 0, '<': 0, '<?xml version=': 0, '>': 0, 'https://': 0, 'lorem ipsum': 0, 'www.': 0, 'xml': 0}, 'pii_count': 0, 'substrings_counts': 0, 'word_list_counts': {'cursed_substrings.json': 1, 'profanity_word_list.json': 0, 'sexual_word_list.json': 0, 'zh_pornsignals.json': 0}}
Ruthenium-Catalyzed Direct Cross-Coupling of Secondary Alcohols to β-Disubstituted Ketones

The β-disubstituted ketone functionality is prevalent in biologically active compounds and in pharmaceuticals. A ruthenium-catalyzed direct synthesis of β-disubstituted ketones by cross-coupling of two different secondary alcohols is reported. This new protocol was applied to the synthesis of variety of β-disubstituted ketones from various cyclic, acyclic, symmetrical, and unsymmetrical secondary alcohols. An amine–amide metal–ligand cooperation in a Ru catalyst facilitates the activation and formation of covalent bonds in selective sequences to provide the products. Kinetic and deuterium-labeling experiments suggested that aliphatic alcohols oxidize faster than benzylic secondary alcohols. A plausible mechanism is proposed on the basis of mechanistic and kinetic studies. Water and H2 are the only byproducts from this selective cross-coupling of secondary alcohols.1 Introduction2 Catalytic Self- or Cross-Coupling of Alcohols and Selectivity Challenges3 Recent Developments in the Synthesis of β-Disubstituted Ketones4 Scope of Ruthenium-Catalyzed Cross-Couplings of Secondary Alcohols5 Mechanistic Studies and Proposed Mechanism6 Conclusion