title: Carbolithiation of S-alkenyl-N-aryl thiocarbamates: carbanion arylation in a connective route to tertiary thiols.
abstract: S-alkenyl-N-arylthiocarbamates are formed from allylic alcohols by sigmatropic rearrangement and isomerization or C═C bond cleavage. They undergo carbolithiation with a range of organolithium reagents, generating benzyllithium intermediates in a stereospecific manner which may undergo N to C aryl migration to yield thiocarbamates with tertiary substituents. A simple base-promoted alcoholysis reveals a series of hindered tertiary thiols with branched carbon skeletons.
authors.affiliation: School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, UK.
authors.forename: Daniele
authors.initials: D
authors.lastname: Castagnolo
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Foley
authors.forename: Hatice
authors.initials: H
authors.lastname: Berber
authors.forename: Renzo
authors.initials: R
authors.lastname: Luisi
authors.forename: Jonathan
authors.initials: J
authors.lastname: Clayden
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D018020:Lithium Compounds / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013859:Thiocarbamates / Q000737:chemistry*
chemical_list: D000475:Alkenes; D018020:Lithium Compounds; D013438:Sulfhydryl Compounds; D013859:Thiocarbamates