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Cross-couplings of unconventional electrophiles with earth-abundant metals

Chenniappan, Vinoth Kumar
Transition metal catalyzed cross-coupling reactions are a reliable and robust approach forperforming bond formation with high selectivity, predictable connectivity patterns, and versatilityto form C-C and C-heteroatom bonds in numerous variations. As a result of this cross-couplingreactions have become an invaluable tool in the synthesis of complex molecules and have foundwide spread use in the synthesis of drug candidates, materials, and natural products. While thisapproach is formidable in forming Csp2-Csp2 bonds, current systems have limitations in formingCsp2-alkyl and alkyl-alkyl bonds. In addition, most of these methods utilize precious metals andpreformed organometallic reagents which is not sustainable. As a means to expand the scope ofcross-coupling partners and meet society's ever growing need for sustainability, our group hasbeen developing cross-coupling methods utilizing earth abundant metals. This dissertation willcover our progress in developing cross-couplings with in situ generated organo-titanium reagents,titanacycles, our dual catalytic Ni/Ti method for cross-coupling nitriles, Ni-catalyzed crosscoupling of alcohols, and our endeavors in photocatalysis.