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Chelation-controlled additions to α-silyloxy aldehydes: an autocatalytic approach.

Title: Chelation-controlled additions to α-silyloxy aldehydes: an autocatalytic approach.
Authors: Raffier L; P. Roy and Diana T. Vagelos Laboratories, University of Pennsylvania , Department of Chemistry, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, United States.; Stanton GR; Walsh PJ
Source: Organic letters [Org Lett] 2013 Dec 20; Vol. 15 (24), pp. 6174-7. Date of Electronic Publication: 2013 Nov 19.
Publication Type: Journal Article; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, Non-P.H.S.
Language: English
Journal Info: Publisher: American Chemical Society Country of Publication: United States NLM ID: 100890393 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1523-7052 (Electronic) Linking ISSN: 15237052 NLM ISO Abbreviation: Org Lett Subsets: MEDLINE
Imprint Name(s): Original Publication: Washington, DC : American Chemical Society, c1999-
MeSH Terms: Alcohols/*chemical synthesis ; Aldehydes/*chemistry; Alcohols/chemistry ; Catalysis ; Molecular Conformation ; Stereoisomerism
Abstract: The Felkin-Anh model has been widely accepted to describe stereochemical outcomes in nucleophilic additions to α-silyloxy carbonyl compounds. Herein, it is demonstrated that chelation-controlled additions can be performed using dialkylzinc reagents in the presence of chlorotrimethylsilane with good to excellent diastereoselectivities. Ethyl zinc chloride, the Lewis acid responsible for promoting chelation, is generated in situ in an autocatalytic fashion. This approach circumvents its use in stoichiometric amounts.
Substance Nomenclature: 0 (Alcohols); 0 (Aldehydes)
Entry Date(s): Date Created: 20131121 Date Completed: 20140224 Latest Revision: 20131220
Update Code: 20260130
DOI: 10.1021/ol4030259
PMID: 24252100
Database: MEDLINE

Journal Article; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, Non-P.H.S.