We are interested in the enantioselective synthesis of complex, physiologically active natural products. To this end, we are interested in developing new organic reactions, and in using computational methods to understand stoichiometric and catalytic organometallic chemistry. Some representative projects include:

(-)-Cameroonan-7α-ol
Using a method we developed, Rh(II) catalyzed intramolecular C-H insertion of an α-diazo ketone 1, readily available from commercial enantiomerically-pure citronellal, delivered 2. Overall in the synthesis of (-)-Cameroonan-7α-ol 3, seven C-H bonds were converted to C-C bonds.

(±)-Cermizine C
We found that the anion from deprotonation of 2-methylpyridine 4 added efficiently to 5 to give the adduct 6. Reduction and cyclization converted 6 into (±)-Cermizine C 7.

Fe-Mediated Cyclocarbonylation
Heating the tosylhydrazone of the ω-dienyl ketone 8 to reflux in xylene in the presence of K₂CO₃ delivered the bicyclic diazene, that lost N₂ spontaneously to give the cyclopropane 9. Cyclocarbonylation to 10 was effected by irradiation in the presence of Fe(CO)₅. This appears to be a generally useful method for the construction of 6,5- and 6,6-bicyclic enones with control of both relative and absolute configuration.