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二氟卡宾生成 SCF 的非常规机理见解：F 标记的 α-SCF 羰基化合物的制备。

An Unconventional Mechanistic Insight into SCF Formation from Difluorocarbene: Preparation of F-Labeled α-SCF Carbonyl Compounds.

机构信息

Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.

School of Pharmaceutical Science and Technology, Tianjin University, 92 Weijin Road, Nankai District, Tianjin, 300072, China.

出版信息

Angew Chem Int Ed Engl. 2017 Mar 13;56(12):3196-3200. doi: 10.1002/anie.201611761. Epub 2017 Feb 14.

DOI:10.1002/anie.201611761
PMID:28194833
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5582945/
Abstract

Trifluoromethylthiolation by sulfuration of difluorocarbene with elemental sulfur is described for the first time, which overrides long-standing trifluoromethyl anion-based theory. Mechanistic elucidation reveals an unprecedented chemical process for the formation of thiocarbonyl fluoride and also enables transition-metal-mediated trifluoromethylthiolation and [ F]trifluoromethylthiolation of α-bromo carbonyl compounds with broad substrate scope and compatibility.

摘要

首次描述了二氟卡宾与单质硫的硫化反应进行三氟甲基化，这推翻了长期以来基于三氟甲基阴离子的理论。机理研究揭示了一种前所未有的形成硫代羰基氟的化学过程，并且还能够实现过渡金属介导的α-溴羰基化合物的三氟甲基硫代化和[F]三氟甲基硫代化，具有广泛的底物范围和兼容性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9043/5582945/bc8c2b0f111d/nihms899617f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9043/5582945/399e8933c872/nihms899617f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9043/5582945/77145ab0586a/nihms899617f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9043/5582945/f339b52c57a4/nihms899617f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9043/5582945/69e07bd4b9b7/nihms899617f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9043/5582945/aeb0e9e1458e/nihms899617f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9043/5582945/bc8c2b0f111d/nihms899617f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9043/5582945/399e8933c872/nihms899617f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9043/5582945/77145ab0586a/nihms899617f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9043/5582945/f339b52c57a4/nihms899617f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9043/5582945/69e07bd4b9b7/nihms899617f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9043/5582945/aeb0e9e1458e/nihms899617f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9043/5582945/bc8c2b0f111d/nihms899617f6.jpg

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