Division of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan.
Chem Commun (Camb). 2023 Feb 28;59(18):2532-2540. doi: 10.1039/d2cc03950h.
Difluorocarbene is a simple and versatile one-carbon unit for synthesizing acyclic and cyclic organofluorine compounds. However, the use of difluorocarbene in organic synthesis has been relatively limited because of the harsh conditions required for its generation, the toxicity of the precursors, and undesired dimerization. This feature article provides an account of (i) the generation of free and metal difluorocarbenes from trimethylsilyl 2,2-difluoro-2-(fluorosulfonyl)acetate (TFDA) or BrCFCOLi/Na and (ii) their application to the facile synthesis of valuable organofluorine compounds. The difluorocarbenes thus generated react with (thio)carbonyl compounds and silyl dienol ethers to provide a wide variety of products such as (a) difluoromethyl (thio)ethers, (b) fluorinated thiophenes, (c) fluorinated thia/oxazoles, (d) fluorinated cyclopentanones and (e) difluoroalkenes.
二氟卡宾是一种简单而多功能的一碳单元，可用于合成无环和环状有机氟化合物。然而，由于其生成所需的苛刻条件、前体的毒性和不希望的二聚化，二氟卡宾在有机合成中的应用相对有限。本文综述了（i）从三甲基硅基 2,2-二氟-2-（氟磺酰基）乙酸酯（TFDA）或 BrCFCOLi/Na 生成游离和金属二氟卡宾，以及（ii）其在易合成有价值的有机氟化合物中的应用。生成的二氟卡宾与（硫）羰基化合物和硅基二烯醇醚反应，提供了各种产物，如（a）二氟甲基（硫）醚，（b）氟化噻吩，（c）氟化噻唑/噁唑，（d）氟化环戊酮和（e）二氟烯烃。
