ENANTIOSELECTIVE ORGANOCATALYTIC CONJUGATE ADDITION FOR THE SYNTHESIS OF δ-SUBSTITUTED CYCLOHEXENONES AND ACYCLIC QUATERNARY ALL-CARBON CENTERS
Organocatalyzed reactions have become prominent in the synthesis of natural products, pharmaceutical drugs, and other industrially useful materials in the last few decades. 2,2-Bi-1-naphthol (BINOL) and its derivatives are unnatural chiral diol organocatalysts which have been used in many enantioselective reactions. For instance, Chong, Schaus, Goodman, and our group found that a BINOL catalyst with electron-withdrawing substituents enhanced reactivity with organoboronate nucleophiles to afford chiral products. First two chapters on this dissertation are to further explore the utility of an asymmetric BINOL catalyzed tandem reaction: (1) Conjugate addition and aldol condensation to synthesize δ-substituted cyclohexenones and (2) Synthesis of acyclic quaternary centers. The third chapter is mainly focused on the synthesis of tertiary boron compounds via photo-induced activation to tosylhydrazone. The formal Barluenga-Valdes coupling was developed decades ago. Under thermal conditions, the C-B bond is typically cleavage from the organoboronate product. Instead, this chapter is exploring the exploitation of this intermediate by using photoactivation conditions.