UCLA

Chapter one provides a survey of the wide variety of unconventional phenol derivatives that are now available for use in traditional cross-coupling reactions. Emphasis is given to carbon-carbon (C-C) bond forming reactions with a brief discussion of other transformations. Chapters two and three are a discussion of our work in the field of nickel-catalyzed cross-coupling reactions of phenol derivatives. The use of aryl pivalates, sulfamates, carbamates, and carbonates in the nickel-catalyzed Suzuki-Miyaura coupling is described, along with synthetic applications utilizing these phenol derivatives. A computational and experimental mechanistic study for the cross-coupling of aryl sulfamates and carbamates is also reported.

Chapters four and five detail our efforts in the total synthesis of the welwitindolinone natural products. The enantiospecific total syntheses of (-)-N-methylwelwitindolinone C isothiocyanate and (-)-N-methylwelwitindolinone C isonitrile, as well as their respective C3-hydroxylated analogs are reported. The synthetic routes feature an aryne cyclization to rapidly construct the [4.3.1]-bicyclic core of these molecules, as well as a late-stage intramolecular nitrene insertion to functionalize a bridgehead carbon. The strategic use of a deuterium kinetic isotope effect to improve the efficiency of the nitrene insertion is also discussed. A computational prediction for the stereochemical configuration at C3 of the hydroxylated welwitindolinones is presented, which was subsequently confirmed by experimental studies.