Carbon–Carbon, Carbon–Oxygen, or Carbon–Nitrogen Bond Formation via 3,3- or 1,3-Rearrangements of O-Vinyl
thesisposted on 2016-02-25, 00:00 authored by Heng-Yen Wang
Rearrangements of N–O bonds have been employed in the development of new methods for the preparation highly functionalized molecules. Specifically, [1,3]- and [3,3]-rearrangements of O-vinyl oximes and O-vinyl hydroxamates have been designed to provide new routes to important synthetic intermediates such as α-oxygenated, α-arylated, and α-aminated ketones as well as privileged medicinally relevant structures such as highly substituted pyrroles and indoles. Two simple routes to O-vinyl oximes and O-vinyl hydroxamates have been developed through the iridium-catalyzed isomerization of O-allyl oxime ethers and the C–O bond coupling of oximes and hydroxamic acids with vinyl boronic acids. These complimentary methods allow for the practical application of the [1,3]- and [3,3]-rearrangements of N–O bonds from simple starting materials. The new processes described in this thesis will promote the development of new retrosynthetic strategies for the preparation of challenging C–C, C–O, and C–N bonds in synthetic targets as well as simplify the preparation of structural derivatives through bypassing the road blocks and limitations of traditional synthetic methods. Mechanistic data has been collected and discussed for all new transformations in order to determine how to further harness and exploit these important new transformations for the relentless demand of new materials and pharmaceutically active compounds.