Studies of the catalytic Mukaiyama aldol reaction utilizing chiral oxazaborolidines : application in the synthesis of substituted butenolides

Abstract

Thesis (Ph. D.)--University of Rochester. Department of Chemistry, 2015.The Corey-Bakshi-Shibata reagent was studied as a catalyst in the formation of butenolides through an asymmetric Mukaiyama type aldol reaction of trimethylsily furans. Multiple variants of the catalyst were tested to determine an optimized catalyst for the desired transformation. The acids used to activate the CBS were also examined in their activation and coordination to the catalyst through temperature dependent proton NMR studies. The reaction conditions were optimized with a 10% catalyst loading and a reagent table compiled determining that the reaction is compatible with both alkyl- and aryl- aldehydes. The scope of the reaction was expended to include other trimethylsilyl enols. Mechanistic studies of the silyl transfer and transition states were also completed