Strategies towards vicinal functionality via carbon-carbon bond-forming reactions

Vicinal functionalities, like 1,2-diols and 1,2-amino alcohols, are highly valuable in synthetic organic chemistry due to both their high representation in natural products, pharmaceuticals, and agrochemicals, as well as their use as synthetic intermediates. The oxidation of alkenes has largely dominated the way synthetic chemists think about installing vicinal functionality, the seminal example being the Sharpless asymmetric dihydroxylation reaction. Herein lies an opportunity to develop a complementary fragment-based coupling strategy, leveraging the vast amounts of preoxidized, affordable biomass starting materials available. Radical activation via photoredox catalysis is an efficient precursor for C–C bond formation. Thus, the work of this dissertation is the development of a photoredox-mediated C–C bond construction strategy to install highly oxidized motifs. In pursuit of this goal, we have been able to demonstrate Giese-coupling on a variety of electron deficient olefins to synthesize 1,2-diols, 1,2-amino alcohols, 1,2-diamines, and 1,2-thiol alcohols. Further expansion of this acetal radical strategy led us to develop a telescoped arylation/activation/substitution strategy towards the combinatorial synthesis of aryl ethanolamines using an acetal radical linchpin. Finally, we have been able to demonstrate the enantioselective synthesis of 1,2,3-triols via a stereochemical memory strategy using inexpensive tartaric acid acetal building blocks.