Catalytic intramolecular hydroarylation of alkenes via directed carbon-hydrogen bond activation

In contemporary organic synthesis, one of the most attractive methods for carbon-carbon bond formation is the transition metal-catalyzed activation and functionalization of otherwise unreactive carbon-hydrogen bonds. Because C-H bonds are among the most ubiquitous and inexpensive chemical linkages in nature, the direct conversion of C-H bonds into C-C bonds represents an efficient and economical strategy for fine chemical production. For this reason, our group has been interested in developing intramolecular C-H activation/alkene insertion reactions that allow rapid access to synthetically useful compounds. This dissertation details our progress toward achieving this goal.; Chapter 1 describes the annulation of aromatic ketones, in which the alkene is tethered at the meta position, which proceeds via ketone-directed C-H bond activation followed by alkene addition to the most hindered ortho site. Although this reaction is both efficient and highly selective, it requires the use of non-isomerizable Akenes, a limitation that can be overcome using imines instead of ketones. Chapter 2 describes the analogous cyclization reaction of aromatic ketimines and aldimines, which is tolerant of various functional groups, different tether lengths, a number of alkene substitution patterns, and the incorporation of heteroatoms in the tether, and which generally proceeds with high selectivity. The work in Chapter 2 constitutes a novel method for the synthesis of functionalized indanes, tetralanes, dihydrobenzofurans, dihydroindoles, and other polycyclic compounds from simple starting materials using directed C-H bond activation.; In spite of substantial recent research activity in the field of C-H activation, examples of catalytic enantioselective reactions involving this chemistry are rare. Chapter 3 details an enantioselective variant of the imine-directed C-H bond functionalization reaction. This work represents the first highly enantioselective catalytic reaction involving aromatic C-H bond activation. Moreover, the newly identified catalyst system enables the intramolecular alkylation reaction to proceed rapidly at temperatures 75°C lower than those required with the previously employed Wilkinson's catalyst.