{'fraction_non_alphanumeric': 0.05062240663900415, 'fraction_numerical': 0.011618257261410789, 'mean_word_length': 5.414893617021277, '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': 0, 'profanity_word_list.json': 0, 'sexual_word_list.json': 0, 'zh_pornsignals.json': 0}}
Synthesis of 3-[(4-nitrophenyl)thio]-substituted 4-methylene-1-pyrrolines from N-propargylic β-enaminones.

A facile and efficient method for the synthesis of 3-[(4-nitrophenyl)thio]-substituted 4-methylene-1-pyrrolines is described. When treated with 4-nitrobenzenesulfenyl chloride in refluxing acetonitrile, N-propargylic β-enaminones produced α-sulfenylated N-propargylic β-enaminones, which in the presence of sodium hydride or cesium carbonate underwent nucleophilic cyclization to afford 4-methylene-3-[(4-nitrophenyl)thio]-1-pyrrolines in good to high yields. It was shown for the first time that on N-propargylic β-enaminone systems, α-sulfenylation dominates over the formation of thiirenium ion. This one-pot two-step process was found to be general for a variety of N-propargylic β-enaminones and demonstrated good tolerance to a diversity of aromatic and heteroaromatic groups with electron-withdrawing and electron-donating substituents. This process is also applicable to the cyclization of internal alkyne-tethered N-propargylic β-enaminones. The enrichment of 1-pyrroline core with an aryl sulfide moiety might exhibit potential for the synthesis of molecules of pharmacological interest.