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.
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页数：7
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