A stereoselective synthesis of 3-aryloctahydroindoles from enantiomerically enriched gamma-nitroketones has been developed. Reduction of imines derived form the nitroketones provides the trans-fused octhaydroindole motif selectively. The cis-octahydroindole skeleton is accessible by an invertive cyclization strategy involving a diastereomerically pure nitromesylate intermediate. This approach was employed in the synthesis of an advanced intermediate to (-)-pancracine. The gamma-nitroketone starting materials are readily available via an organocatalytic Michael reaction.

An efficient route to functionalized indolizidines from an enantiomerically enriched γ‐nitro ketone is described. The nitro ketone is obtained by an organocatalytic, enantioselective ketone‐nitro alkene Michael addition. Oxidative ring expansion of the nitro ketone and subsequent methanolysis provides a 8‐nitro‐4‐oxooctanoate. This is stereoselectively transformed to the key, functionalized indolizidine intermediate which is readily converted to (+)‐ipalbidine and (+)‐antofine.

The efficient, 12-14 step (LLS) total synthesis of (-)-halenaquinone has been achieved. Key steps in the synthetic sequence include: (a) proline sulfonamide-catalyzed, Yamada-Otani reaction to establish the C6 all-carbon quaternary stereocenter, (b) multiple, novel palladium-mediated oxidative cyclizations to introduce the furan moiety, and (c) oxidative Bergman cyclization to form the final quinone ring.

Guanidinyl pyrrolidines derived from 'S'-proline are effective catalysts for the enantioselective conjugate addition of malonate, nitroalkane and other carbon and heteroatom nucleophiles to cyclohexenone and cyclopentenone in the absence of basic additives. The stereoselectivity is strongly dependent on catalyst loading as well as reaction concentration.

A generalized method for accessing highly functionalized amino‐substituted bicyclo[2.2.2]octanes via p‐dodecylphenylsulfonamide catalyst in a good enantio‐ and diastereoselective fashion has been developed. A discussion of the mechanistic underpinnings of this transformation is presented. Finally, an unexpected discovery enabling the extension of this protocol to the synthesis of OH‐substituted bicyclo[2.2.2]octanes with encouraging levels of stereoselectivity is discussed.