ALCOHOL DEOXYGENATION FOR THE SYNTHESIS OF C(sp3) RICH ORGANIC MOLECULES

Abstract

Synthetic methods that enable rapid construction of complex organic molecules fromsimple precursors are of paramount importance to human health. Given their structural diversity and ubiquity amongst a variety of natural sources, harnessing alcohols as starting materials in chemical synthesis would provide access to underexplored chemical space. In particular, cleavage of an alcohol C–O bond and subsequent formation of new C–C bonds represents a powerful strategy for complex molecule synthesis. Traditional deoxygenation protocols require harsh reaction conditions or laborious prefunctionalization that limits their utility. Photoredox catalysis has provided of a suite of methods for the cleavage of alcohol C–O bonds, including the discovery of benzoxazolium salts (termed NHCs) as in situ activating reagents. This thesis describes the utilization of these benzoxazolium salts to convert alcohols to C(sp3)–CF3 and C(sp3)–C(sp3) bonds. Chapter 2 discusses the conversion of alcohols to aliphatic trifluoromethyl groups by merging NHC deoxygenation with copper metallaphotoredox catalysis. Chapter 3 details a first of its kind cross alcohol coupling reaction that is enabled by combining NHC alcohol activation with the principles of SH2 radical sorting.