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Catalytic Asymmetric Generation of (Z)-Disubstituted Allylic Alcohols
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Section:Abstract
A one-pot method for the direct preparation of enantioenriched (Z)-disubstituted allylic alcohols is introduced. Hydroboration of 1-halo-1-alkynes with dicyclohexylborane, reaction with t-BuLi, and transmetalation with dialkylzinc reagents generate (Z)-disubstituted vinylzinc intermediates. In situ reaction of these reagents with aldehydes in the presence of a catalyst derived from (−)-MIB generates (Z)-disubstituted allylic alcohols. It was found that the resulting allylic alcohols were racemic, most likely due to a rapid addition reaction promoted by LiX (X = Br and Cl). To suppress the LiX-promoted reaction, a series of inhibitors were screened. It was found that 20−30 mol % tetraethylethylenediamine inhibited LiCl without inhibiting the chiral zinc-based Lewis acid. In this fashion, (Z)-disubstituted allylic alcohols were obtained with up to 98% ee. The asymmetric (Z)-vinylation could be coupled with tandem diastereoselective epoxidation reactions to provide epoxy alcohols and allylic epoxy alcohols with up to three contiguous stereogenic centers, enabling the rapid construction of complex building blocks with high levels of enantio- and diastereoselectivity.
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This article has been cited by 15 ACS Journal articles (5 most recent appear below).
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Overriding Felkin Control: A General Method for Highly Diastereoselective Chelation-Controlled Additions to α-Silyloxy Aldehydes
Gretchen R. Stanton, Corinne N. Johnson and Patrick J. WalshJournal of the American Chemical Society2010 132 (12), 4399-4408Overriding Felkin Control: A General Method for Highly Diastereoselective Chelation-Controlled Additions to α-Silyloxy Aldehydes
Gretchen R. Stanton, Corinne N. Johnson and Patrick J. WalshJournal of the American Chemical Society2010 132 (12), 4399-4408According to the Felkin−Anh and Cram-chelation models, nucleophilic additions to α-silyloxy aldehydes proceed through a nonchelation pathway due to the steric and electronic properties of the silyl group, giving rise to Felkin addition products. Herein we ...
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History
- Published In Issue December 26, 2007
- Received August 17, 2007
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