Abstract

Two new cascade transformations of α,β-unsaturated thioesters catalyzed by amidine-based catalysts have been developed. First, a reagent-free transformation of o-formylaryl cinnamoyl thioesters catalyzed by HBTM-2 to produce 2-substituted thiochromenes achieved high enantioselectivities and yields while forming carbon dioxide as the only byproduct. Second, a highly diastereo- and enantioselective tandem rearrangement of less reactive enone thioesters into tricyclic thiochromanes in the presence of electron-rich amidine-based catalysts was developed. These catalysts were designed with the help of DFT calculations. H-PIP, the first chiral amidine-based catalyst synthesized in our group, performed the best overall in the thiochromane synthesis.The second chapter of this thesis describes the design of chiral ligands using the Cl-PIQ structure as a building block. A new class of fused imidazoline ligands was synthesized from 2-chloro-3-quinolinecarboxaldehyde, and their efficacy was demonstrated by their performance in the asymmetric Henry reaction.

Committee Chair

Vladimir B. Birman

Committee Members

Jonathan C. Barnes, Alexei V. Demchenko, Liviu M. Mirica, Kevin D. Moeller,

Comments

Permanent URL: https://doi.org/10.7936/K71R6PXS

Degree

Doctor of Philosophy (PhD)

Author's Department

Chemistry

Author's School

Graduate School of Arts and Sciences

Document Type

Dissertation

Date of Award

Winter 12-15-2017

Language

English (en)

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