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An Arylation Strategy to Propargylamines: Catalytic Asymmetric Friedel–Crafts‐type Arylation Reactions of C‐Alkynyl Imines
Author(s) -
Wang Yingcheng,
Jiang Liang,
Li Long,
Dai Jun,
Xiong Dan,
Shao Zhihui
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201608918
Subject(s) - friedel–crafts reaction , chemistry , electrophile , catalysis , combinatorial chemistry , alkynylation , alkylation , phosphoric acid , organic chemistry
The first arylation strategy for the synthesis of enantioenriched propargylamines is disclosed. This approach, which is complementary to previous alkynylation and alkylation strategies, involves a C(sp 2 )−C(sp 3 ) bond formation, and is based on the first asymmetric Friedel–Crafts‐type arylation reaction of C‐alkynyl imines. Asymmetric Friedel–Crafts reactions with electron‐deficient phenols, a longstanding unsolved challenge, have thus been realized for the first time, enabled by the combination of our recently introduced C‐alkynyl N‐Boc‐protected N,O‐acetals as electrophiles and chiral phosphoric acids as catalysts. The synthetic utility of the resulting structurally diverse and polyfunctional chiral propargylamines was demonstrated by a series of selective transformations, including controlled reduction of the alkynyl group and iterative cross‐couplings.