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Title:On the Stereochemistry of Allylmetal-Aldehyde Condensations (Allyltrimethylsilane, Allyltributylstannane, Homoallylic Alcohols)
Author(s):Weber, Eric John
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Organic
Abstract:The stereochemical course of the intramolecular allylmetal-aldehyde condensation of allylsilane 3a, allylstannane 3b, and pentadienylsilane 6 has been investigated. A modest preference for the syn isomer 4 arising from a synclinal orientation of double bonds was observed with the Lewis acid catalyzed reaction of 3a. The selectivity for 4 was dependent on Lewis acid. Cyclization induced by fluoride ion resulted in a stereochemical reversal. The Lewis acid and heat induced cyclization of 3b gave a large preference for the syn isomer 4 which was interpreted in terms of an intrinsic stereoelectronic preference for a synclinal orientation of reacting double bonds in the transition state. The Lewis acid catalyzed cyclization of 6 gave a modest preference for the syn isomer 4. The syn-selectivity was independent of Lewis acid.
Issue Date:1985
Description:128 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1985.
Other Identifier(s):(UMI)AAI8521900
Date Available in IDEALS:2014-12-15
Date Deposited:1985

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