Copper-Catalyzed Intramolecular Radical Amination of Tertiary C(sp3)-H Bonds to Access α-Quaternary Pyrrolidines

Herein, we describe a Cu(I)/phosphoric acid catalyzed intramolecular radical tertiary C(sp(3))-H amination of N-chlorosulfonamide, providing an applicable route to the pyrrolidine structural motifs bearing an alpha-quaternary stereocenter (>20 examples with up to 94 % yield). Mechanistic studies...

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Bibliographic Details
Published inAsian journal of organic chemistry Vol. 12; no. 7
Main Authors Gao, Ang, Ren, Yang-Qing, Luan, Cheng, Tian, Yu, Liu, Lin, Gu, Qiang-Shuai, Li, Zhong-Liang, Yang, Chang-Jiang, Liu, Xin-Yuan
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 01.07.2023
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
DISTAL
pyrrolidine
STRATEGY
radical reaction
AZOMETHINE YLIDES
SHIHUNINE
HYDROAMINATION
C-H functionalization
FUNCTIONALIZATION
copper catalysis
ALKENES
AMINES
amination
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Summary:Herein, we describe a Cu(I)/phosphoric acid catalyzed intramolecular radical tertiary C(sp(3))-H amination of N-chlorosulfonamide, providing an applicable route to the pyrrolidine structural motifs bearing an alpha-quaternary stereocenter (>20 examples with up to 94 % yield). Mechanistic studies indicate that the reaction involves an intramolecular 1,5-hydrogen atom transfer process to form the key tertiary C-centered radical followed by a C-N bond formation. The corresponding enantioselective amination is accordingly disclosed by Cu(I)/chiral phosphoric acid catalyst to afford the chiral products with up to 81 % enantiomeric excess (ee). This strategy is anticipated to facilitate the development of tertiary C(sp(3))-H functionalization.
ISSN:2193-5807
2193-5815
DOI:10.1002/ajoc.202300220