Zhao Peng, Liu Mengting, Li Ying, Wang Lili, Duan Zheng
College of Chemistry, International Phosphorus Laboratory, Zhengzhou University, Zhengzhou 450001, China.
J Org Chem. 2024 Oct 4;89(19):14305-14314. doi: 10.1021/acs.joc.4c01720. Epub 2024 Sep 24.
New reactions of benzyl phosphine oxide/sulfide with oxalyl chloride are presented. The resulting reactive intermediates, acyl chloride-substituted chlorophosphonium ylides, are capable of undergoing esterification and Friedel-Crafts acylation reactions, ultimately yielding either methyl 2-(2-bromophenyl)-2-(diphenylphosphoryl)acetate or β-carbonyl-diarylphosphine oxide derivatives. Additionally, when an alkynyl group is contained in the acyl chloride-substituted chlorophosphonium ylide, intramolecular cyclization occurs, leading to the formation of a pair of and dichlorophosphonyl benzofulvene isomers. The generation process of acyl chloride-substituted chlorophosphonium ylide was carefully monitored by using P{H} NMR spectroscopy, and a plausible reaction mechanism was proposed.
本文介绍了苄基氧化膦/硫化物与草酰氯的新反应。生成的反应中间体，即酰氯取代的氯代鏻叶立德，能够进行酯化反应和傅克酰基化反应，最终生成2-(2-溴苯基)-2-(二苯基磷酰基)乙酸甲酯或β-羰基-二芳基氧化膦衍生物。此外，当酰氯取代的氯代鏻叶立德中含有炔基时，会发生分子内环化反应，生成一对二氯膦酰基苯并富烯异构体。通过使用³¹P{H}核磁共振光谱对酰氯取代的氯代鏻叶立德的生成过程进行了仔细监测，并提出了合理的反应机理。
