A general Fe-catalysed azidation of iododifluoroketones and its utilization for the synthesis of gem-difluoromethylenated triazoles

被引：4

作者：

Wang, Xia ^{[1
,2
]}

Liu, Shixun ^{[1
,2
]}

Xu, Shibo ^{[1
,2
]}

Wu, Shiguang ^{[1
,2
]}

Wu, Jingjing ^{[1
,2
,3
]}

Wu, Fanhong ^{[1
,2
]}

机构：

[1] Shanghai Inst Technol, Sch Chem & Environm Engn, Shanghai 201418, Peoples R China

[2] Shanghai Inst Technol, Shanghai Engn Res Ctr Green Fluoropharmaceut Techn, Shanghai 201418, Peoples R China

[3] Chinese Acad Sci, Shanghai Inst Organ Chem, Key Lab Organofluorine Chem, Shanghai 200032, Peoples R China

来源：

ORGANIC CHEMISTRY FRONTIERS | 2024年 / 11卷 / 07期

基金：

中国国家自然科学基金;

关键词：

ORGANIC AZIDES; NITROGEN BONDS; ATOM-TRANSFER; SODIUM-AZIDE; FLUORINE; KETONES; ALKENES; CARBON; DIFLUOROALKYLATION; DIFLUOROCARBENE;

D O I：

10.1039/d3qo02088f

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

An iron-catalysed radical azidation of iododifluoroketones with TMSN3 was developed under mild reaction conditions, providing a concise synthesis of alpha-difluoroalkylazides. The methyl radical generated from tert-butyl peroxybenzoate enables the XAT (halogen atom transfer) process to give gem-difluoromethylenyl radical, which underwent outer-sphere radical azidation to render the otherwise challenging CF2-N bond formation with the assistance of iron catalyst. This protocol tolerates both difluoroacetophenone and difluoroketone derivatives with good to excellent yields. The resulting difluorinated azides could be readily transformed into the structurally important triazolyl difluoroketones via the copper(i)-catalysed azide-alkyne cycloaddition (CuAAC), allowing a modular synthesis of CF2-derived N-containing heterocycles.

引用

页码：2054 / 2061

页数：8