Design and Development of Novel Methods for C--H Functionalization for Amination and C--C Bond Formation

Building complex molecules from simple starting materials is the heart of organic chemistry. Recently, the functionalization of generally unreactive C--H bonds has been a common target for such transformations due to their ubiquity and the atom economy associated with the transition. A family of ruthenium(II) 2,6-bis(imido)pyridyl complexes was developed for the intermolecular C--H amination of benzylic C--H bonds using sulfamate esters in a racemic fashion. A chiral derivative of the bisimidopyridyl ligand framework was proposed and progress was made toward its synthesis. Separately, molecular recognition was also explored as a means of inducing enantioselectivity in C-- H amination reactions. A pyridinebisoxazoline-derived ligand was proposed and progress was made toward its synthesis. Carbon-carbon bond forming reactions for coupling aryl rings are of interest to the medicinal and materials communities. Methodology for the direct coupling of benzobisthiazoles and aryl halides using a copper/palladium co-catalytic system was developed and optimized, and the substrate scope was explored. This was expanded to the synthesis of cruciform structures and the functionalization of thiazolothiazole. Dehydrogenative carbon-carbon bond forming methodology for the synthesis of thiophene substituted benzothiazole derivatives was developed.