Part I. Stereochemical Studies on the Addition of Allylsilanes to Aldehydes. Part II. Stereochemical Studies on the Addition of Allylmetal Reagents to Acetals

Systematic investigations have been performed to determine the mechanism and origin of selectivity of the allylmetal-aldehyde reaction. Initial studies were performed to determine the solution structure of Lewis acid-aldehyde complexes. The intramolecular allylmetal-aldehyde reaction was next studied using three different model systems. The first two model systems were investigated to determine the relative disposition of double bonds in the transition structure of the allylmetal-aldehyde condensation. The next model system incorporated a deuterium label to allow an unbiased assessment of the syn versus anti S$\sb{\rm E}\sp\prime$ pathways. The cyclizations of the model systems were performed with several Lewis acids. The size of the Lewis acid-aldehyde complex significantly affected the relative orientation of the double bonds. Cyclization of the deuterium-labeled model system proceeded with high selectivity via an anti S$\sb{\rm E}\sp\prime$ pathway regardless of the proximal/distal ratio of products for all Lewis acids studied.

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 dc:creator

• Almstead, Neil Gregory

Contributors dc:contributor

• Denmark, S.E.,

• Chemistry, Organic

Identifier

(UMI)AAI9305449

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/72271