Novel silyl migration -mediated bond -forming reactions: Applications in organic synthesis
Abstract
The development and application of novel silyl migration-mediated bond-forming reactions is described. The primary objective of this research was to develop applications in which the silyl group not only facilitated multiple bond-forming steps, but also provided opportunities for stereocontrol of the overall transformation. A subsequent objective was to further the mechanistic understanding of the Brook rearrangement and demonstrate its utility in synthetic applications. Two key transformations were explored: the silicon-mediated Baylis-Hillman reaction and silyl migration-mediated bis-functionalizations of arene complexes. A highly efficient method for the generation of α-methylene-β-hydroxycarbonyl compounds from aryl vinyl ketones has been developed. This new methodology successfully addressed the issue of rapid head-to-tail dimerization that is encountered when aryl vinyl ketones are utilized as Baylis-Hillman substrates. Because of their utility, these novel adducts are appealing substrates for synthetic applications, including biologically important compounds. The use of silyl migrations as a general and efficient method for achieving multiple stereoselective bond formations has also been achieved. This successful strategy provides a compelling method to access highly functionalized arene chromium tricarbonyl complexes in a single step. The general strategy involves a tandem alkylation/silyl migration/inter- or intramolecular trapping sequence. The strategy appears to possess significant potential for the asymmetric synthesis of spirocyclic ring systems, including fredericamycin A.
Degree
Ph.D.
Advisors
Moser, Purdue University.
Subject Area
Organic chemistry
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