M. Bhupathy

Remarkable stereocontrol in the addition of an anion to an α- alkoxyaldehyde by encouraging or discouraging internal complexation. Applications to brief syntheses of the mus musculus (house mouse) pheromone and exo-brevicomin

Abstract Stereoselective addition of ethylmetallic reagents to acrolein dimer 1 and the conversion of the threo alchol 4t to exo -brevicomin and the Mus musculus pheromone are reported.

Highly efficient terpenoid pheromone syntheses via regio and stereocontrolled processing of allyllithiums generated by reductive lithiation of allyl phenyl thioethers

Abstract Previous work had shown that reducuve lithiation of allyl phenyl thioethers, followed by transmetallation, produces allylmetallics which react selectively with carbonyl compounds at the most or least substituted terminus; the latter results in mainly cis olefin. This technology allows extremely efficient syntheses of racemic versions of lavandulol (two-pot, 70% yield), the Comstock mealy bug pheromone (one-pot, 45% yield) and the California red scale pheromone (4-steps, 23% yield).

Carbenoid type base induced ring expansion of the adducts of cyclic ketones with bis(phenylthio)methyllithium

In another application of the principle that metallo derivatives of bis(phenylthio)acetals behave as carbenoids when present in the same molecule with another anionic group, the adducts of cyclic ketones with bis(phenylthio)methyllithium react with an alkyllithium to yield the ring expanded α-(phenylthio) ketones.

1-Phenylthio-1-(trimethylsiloxy)cyclopropanes via the sila-Pummerer rearrangement

Abstract This first study of the sila-Pummerer rearrangement in a cyclopropane system reveals that several 1-trimethylsiloxy-1 -(phenylthio)cyclopropanes can be prepared stereoselectively through putative sulfur-stabilized carbocationic intermediates.

1-Methoxy-1-(phenylthio)cyclopropanes from olefins via the Pummerer rearrangement

Abstract The Pummerer rearrangements of cyclopropyl(methoxy)phenylsulfonium salts proceed via sulfur-stabilized carbocations to yield the title compounds. The sulfonium salts were prepared in high yields from olefins via carbene addition, oxidation, and methylation.

A one-flask, high-yield, stereoselective synthesis of racemic endo-brevicomin

Abstract Treatment of acrolein dimer sequentially with three molar equivalents of ethyllithium and excess methyl iodide followed by aqueous acidic workup provides brevicomin in 69% yield as a 4:1 mixture of endo and exo isomers; a modification allows preparation of a mixture richer in the exo-isomer.