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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 international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201607828
Subject(s) - enantioselective synthesis , catalysis , chemistry , organic chemistry , combinatorial chemistry , organocatalysis
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.