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Extremely Active Organocatalysts Enable a Highly Enantioselective Addition of Allyltrimethylsilane to Aldehydes
Author(s) -
Kaib Philip S. J.,
Schreyer Lucas,
Lee Sunggi,
Properzi Roberta,
List Benjamin
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201607828
Subject(s) - enantioselective synthesis , catalysis , chemistry , organic chemistry , organocatalysis , combinatorial chemistry
Abstract The enantioselective allylation of aldehydes to form homoallylic alcohols is one of the most frequently used carbon–carbon bond‐forming reaction in chemical synthesis and, for several decades, has been a testing ground for new asymmetric methodology. However, a general and highly enantioselective catalytic addition of the inexpensive, nontoxic, air‐ and moisture‐stable allyltrimethylsilane to aldehydes, the Hosomi–Sakurai[1][A. Hosomi, 1976] reaction, has remained elusive.[2][D. R. Gauthier, 1996], [3][, ] Reported herein is the design and synthesis of a highly acidic imidodiphosphorimidate motif (IDPi), which enables this transformation, thus converting various aldehydes with aromatic and aliphatic groups at catalyst loadings ranging from 0.05 to 2.0 mol % with excellent enantioselectivities. Our rationally constructed catalysts feature a highly tunable active site, and selectively process small substrates, thus promising utility in various other challenging chemical reactions.