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Enantioselective α‐Benzylation of Acyclic Esters Using π‐Extended Electrophiles
Author(s) -
Schwarz Kevin J.,
Yang Chao,
Fyfe James W. B.,
Snaddon Thomas N.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201806742
Subject(s) - electrophile , chemistry , enantioselective synthesis , alkylation , nucleophile , lewis acids and bases , catalysis , phosphate , combinatorial chemistry , organic chemistry , stereochemistry
The first asymmetric cooperative Lewis base/palladium catalyzed benzylic alkylation of acyclic esters is reported. This reaction proceeds via stereodefined C1‐ammonium enolate nucleophiles. Critical to its success was the identification of benzylic phosphate electrophiles, which were uniquely reactive. Alkylated products were obtained with very high levels of enantioselectivity, and this method has been applied toward the synthesis of the thrombin inhibitor DX‐9065a.