TMSCF2Br-Enabled Fluorination-Aminocarbonylation of Aldehydes: Modular Access to α-Fluoroamides

被引：34

作者：

Liu, An ^{[1
]}

Ni, Chuanfa ^{[1
]}

Xie, Qiqiang ^{[1
]}

Hu, Jinbo ^{[1
]}

机构：

[1] Chinese Acad Sci, Univ Chinese Acad Sci, Shanghai Inst Organ Chem, Ctr Excellence Mol Synth,Key Lab Organofluorine C, 345 Ling Ling Rd, Shanghai 200032, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2022年 / 61卷 / 08期

基金：

中国国家自然科学基金;

关键词：

Amide; Aminocarbonylation; Ammonium ylide; Difluorocarbene; Fluorination; C-F BOND; HETEROARYL-N-DIFLUOROMETHYL; AZOMETHINE YLIDES; 1,3-DIPOLAR CYCLOADDITION; O-DIFLUOROMETHYLATION; CATALYZED SYNTHESIS; CARBONYL-COMPOUNDS; DIFLUOROCARBENE; ACID; DIFLUOROOLEFINATION;

D O I：

10.1002/anie.202115467

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A protocol for the modular assembly of the alpha-fluoroamide motif has been developed, which provides a practical method for the efficient synthesis of structurally diverse alpha-fluoroamides from easily available aldehydes and tertiary amines through a three-component fluorination-aminocarbonylation process. The key to the success of this process is taking advantage of the multiple roles of the unique difluorocarbene reagent TMSCF2Br (TMS=trimethylsilyl). The mechanism of the process involves the 1,2-fluorine and oxygen migrations of the in situ formed TMS-protected alpha-aminodifluoromethyl carbinol intermediates, which represents a new type of deoxyfluorination reaction.

引用

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