title: Tertiary thiols from allylic thiocarbamates by tandem enantioselective [3,3]-sigmatropic rearrangement and stereospecific arylation.
abstract: The synthesis of tertiary thiols in enantiomerically enriched form is accomplished by lithiation of enantiomerically enriched N-aryl allylic thiocarbamates. Formation of an allyllithium derivative promotes intramolecular N to C aryl migration to the position α to sulfur, generally with good stereospecificity. The substrates may themselves be obtained by Pd-catalyzed enantioselective [3,3]-sigmatropic rearrangement of N-aryl O-allyl thiocarbamates. Solvolysis of the product thiocarbamates yields tertiary thiols, which may be converted to sulfide derivatives.
authors: School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, U.K.
authors: Gaëlle
authors: G
authors: Mingat
authors: Paul
authors: P
authors: MacLellan
authors: Marju
authors: M
authors: Laars
authors: Jonathan
authors: J
authors: Clayden