Malcolm R. Binns

HMPA-Mediated conjugate addition of alkyl- and phenylthioallyl anions to cyclopentenone

Abstract One equivalent of HMPA induces 1,4-addition of the title anions predominantly through the α -position to cyclopentenone in THF at −78°. In THF alone irreversible addition takes place to give mixtures comprising largely α and γ -1,2 products.

Preparation of stable, camphor-derived, optically active allylic sulfoxides

Abstract (+)-Camphor has been stereospecifically converted in three steps into a single isoborneol allyl sulfoxide derivative, which upon heating to 145° is quantitatively converted into its sulfoxide epimer; the anions of these compounds undergo stereospecific conjugate addition to cyclopent-2-en-1-one.

The diastereospecific aprotic conjugate addition reactions of carbanions derived from allylic sulfoxides and allylic phosphine oxides

Abstract The title carbanions undergo conjugate addition to cyclic enones in THF to deliver vinylic sulfoxides and vinylic phosphine oxides as single diastereomers.

A route to prostaglandin precursors from 1-(phenylthio)-2-octenyllithium.

The enolates generated by the conjugate addition of 1-(phenylthio)-2-octenyllithium to 4-tert-butoxycyclopent-2-en-1-one and <-crotonolactone react with methyl 7-halohept-5-ynoates in the presence of Ph3SnCl to deliver products which may be converted into prostaglandin precursors.

The diastereospecific aprotic conjugate addition reactions of allylic anions-mechanistic aspects.

Abstract A ten-membered cyclic “chair-chair” - or “ trans -decalyl”-like TS is proposed to account for the diastereospecific aprotic conjugate addition reactions of allylic carbanions bearing polar, charge-stabilizing groups.