Brian C. Vanderplas

The preparation of β-substituted amines from mixtures of epoxide opening products via a common aziridinium ion intermediate

Abstract Here we describe a one-pot synthesis of a series of β-substituted amines as single enantiomers from an initial regioisomeric mixture of styrene oxide ring-opening products. We also report the isolation and characterization of a key β-chloro intermediate and provide additional insight into the mechanism of the reported alkylations. These results require that the reaction proceeds through a common aziridinium ion intermediate on two separate occasions in order to account for the observed overall net retention of configuration in proceeding from ( S )-styrene oxide to the desired β-substituted amine products.

Efficient synthesis of the κ-opioid receptor agonist CJ-15,161: four stereospecific inversions at a single aziridinium stereogenic center

Abstract An efficient four-step sequence has been developed for the synthesis of the κ-opioid receptor agonist CJ-15,161. The process features four consecutive regioselective and stereospecific inversions at a single aziridinium stereogenic center, which leads to overall retention of stereochemistry, in a single operation. The chemistry is straightforward, practical and amenable to large-scale synthesis.

Synthesis of an optically active octahydro-2H-pyrido[1,2-a]pyrazine based CNS agent

Abstract A synthesis of an optically active octahydro-2H-pyrido[1,2-a]pyrazine is presented. The key sequence involved the equilibration of an optically active cis-aldehyde to give the thermodynamic trans-aldehyde that was trapped by nitromethane anion.

Oxidation of carbamate-protected alkylhydrazines to the corresponding hydrazones under Swern conditions

Abstract Carbamate protected alkylhydrazines have been found to oxidize cleanly to the corresponding hydrazone under Swern conditions. The reaction works on hydrazines with primary, secondary, and branched alkyl groups.