|dc.description.abstract||The work to be presented herein illustrates several important facts. First, the
synthesis of BIBOL (19), a 1,4-diol derived from the monoterpene camphor has allowed
us to demonstrate that oxidative dimerizations of enolates can, and do proceed with nearly
complete diastereoselectivity under kinetically controlled conditions. The yield of BIBOL
is now 50% on average, with a 10% yield of a second diastereomer, which is likely the
result of a non-kinetic hydride reduction, thereby affording the epimeric alcohol, 20,
coupled on the exo face of camphor. This implies the production of 60% of a single
coupling diastereomer. No other diastereomers from the reduction were observed. The
utility of BEBOL has been illustrated in early asymmetric additions of diethylzinc to aryl
aldehydes, with e.e.'s as high as 25-30%. '^'
To further the oxidative coupling work, the same methodology which gave rise to
BIBOL was applied to the chiral pool ketone, menthone. Interestingly, this gave an
excellent yield of the a-halohydrin (31), which is the result of a chlorination of menthone.
This result clearly indicates the high stereoselectivity of the process regardless of the
outcome, and has illustrated an interesting dichotomy between camphor and menthone.
The utility of the chlorination product as a precursor other chiral ligands is currently being
Finally, a new series of 1,3-diols as well as a new aminoalcohol have successfully
been synthesized from highly diastereoselective aldol/mannich reactions. Early studies
have indicated their potential in asymmetric catalysis, while employing pi-stack interactions
as a means of controlling enantioselective aldol reactions.||en_US