Graduation Year

2016

Degree

Ph.D.

Degree Name

Doctor of Philosophy (Ph.D.)

Degree Granting Department

Chemistry

Major Professor

Peter Zhang, Ph.D.

Co-Major Professor

Shengqian Ma, Ph.D.

Committee Member

Mark McLaughlin, Ph.D.

Committee Member

Jon Antilla, Ph.D.

Abstract

Metal-catalyzed cyclopropanation of olefins with diazo reagents is one of the most general and efficient method to prepare cyclopropanes. The resulting cyclopropyl units are found as a basic structural element in a wide range of naturally occurring compounds and biologically active compounds, and can serve as versatile synthetic intermediates in the synthesis of multifunctionalized cycloalkanes and acyclic compounds. Since Co(II) complexes of D2-symmetric chiral amidoporphyrins [Co(D2-Por*)] were first introduced in 2004, Co(II)-metalloradical catalysis (MRC) have emerged as a new platform for asymmetric cyclopropanation. These metalloradical catalysts have been shown to be highly effective for asymmetric intermolecular cyclopropanation of a broad scope of substrates with different diazo reagents, with excellent diastereoselectivity and enantioselectivity.

This dissertation aims to develop new Co(II)-MRC based enantioselective cyclopropanation systems. It will elaborate on three types of stereoselective cyclopropanation reactions from olefins: radical cyclopropanation with α-halodiazoacetates, asymmetric bicyclization of diazoketones, and radical cyclopropanation with fluoroaryl diazomethanes. These three processes will be examined in the context of diastereo- and enantiocontrol. And also, the application of cyclopropanation products have been demonstrated, which could potentially lead to more exciting works.

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