University of Illinois at Urbana-Champaign
On the Stereochemistry of Allylmetal-Aldehyde Condensations (Allyltrimethylsilane, Allyltributylstannane, Homoallylic Alcohols)
Abstract
dc:descriptionThe 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.
Degree
thesis:*- Name thesis:degree_name
- Ph.D.
- Level thesis:degree_level
- Dissertation
- Discipline thesis:degree_discipline
- Chemistry
- Grantor
- University of Illinois at Urbana-Champaign
- Year dc:date
- 2014
Author and committee
dc:creator, dc:contributor.*- Author dc:creator
-
- Weber, Eric John
Subjects
dc:subject × 1Identifiers
dc:identifier.*- Identifier
- (UMI)AAI8521900
- OAI identifier oai:identifier
- oai:www.ideals.illinois.edu:2142/70305