Monofluoromethyl-Substituted Sulfonium Ylides:Preparation,Structure-Reactivity Study and Substrate Scope

• 作者: Xin Hong Yafei Liu Long Lu Qilong Shen
• 来源期刊: 中国化学（英文版）
• 年，卷（期）: 2020,（11）
• 所属期刊栏目: Comprehensive Reports
• 页码范围: 1317-1331
• 页数: 15页
• 语种: 英文
• DOI: 10.1002/cjoc.202000206

摘要

Structure-reactivity study of a family of electrophilic monofluoromethylating reagents based on sul-fonium ylide skeleton with different steric hindrance and electron-withdrawing properties was described.These studies led us to discover two highly reactive reagents 3 with a cyclic malonate backbone and 6 with an electron-poor 1,1,1,5,5,5-hexafluoropentane-2,4-dione backbone.The high reactivity of reagent 6 allowed to highly selectively access either C-monofluoromethylated or O-monofluoromethylated β-ketoesters in high yields by the use of different bases.In addition,reactions of reagent 3 with a variety of nucleophiles including phenols,carboxylic acids,thiophenols or heteroaryl nucleo-philes occurred in full conversion within 10 min at room temperature and the scopes for these reactions were reported in detail.