Date of Graduation
8-2016
Document Type
Dissertation
Degree Name
Doctor of Philosophy in Chemistry (PhD)
Degree Level
Graduate
Department
Chemistry & Biochemistry
Advisor/Mentor
Matt Mcintosh
Committee Member
Neil Allison
Second Committee Member
Bill Durham
Third Committee Member
Feng Wang
Keywords
Pure Sciences, Assymetic synthetic
Abstract
CuIPhEt is a C2-symmetric N-heterocyclic carbene catalyst used in the asymmetric hydrosilylation of a variety of prochiral ketones with good yields and selectivities. The large-scale, five-step synthesis of this carbene has been devised. The second step of the synthetic plan includes a double asymmetric hydrogenation of a 1,1-diaryl alkene—a traditionally difficult transformation. The procedure for the use of CuIPhEt in asymmetric hydrosilylations has been optimized and used on both the originally published substrate scope and new compounds. This protocol for the hydrosilylation has been applied in a 10 g reduction to create an intermediate for use toward the total synthesis of antascomicin B. A class of 2-ketoazoles was synthesized for use in asymmetric hydrosilylations, but only poor selectivities were observed.
Citation
Spahn, E. S. (2016). The Large-Scale Synthesis and Asymmetric Hydrosilylations of CuIPhEt, a C2-Symmetric N-Heterocyclic Carbene. Graduate Theses and Dissertations Retrieved from https://scholarworks.uark.edu/etd/1693