title: Tertiary alcohols by tandem β-carbolithiation and N→C aryl migration in enol carbamates.
abstract: Enol carbamates (O-vinylcarbamates) derived from aromatic or α,β-unsaturated compounds and bearing an N-aryl substituent undergo carbolithiation by nucleophilic attack at the (nominally nucleophilic) β position of the enol double bond. The resulting carbamate-stabilized allylic, propargylic, or benzylic organolithium rearranges with N→C migration of the N-aryl substituent, creating a quaternary carbon α to O. The products may be readily hydrolyzed to yield multiply branched tertiary alcohols in a one-pot tandem reaction, effectively a polarity-reversed nucleophilic β-alkylation-electrophilic α-arylation of an enol equivalent.
authors: School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
authors: Anne M
authors: AM
authors: Fournier
authors: Jonathan
authors: J
authors: Clayden
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D000478:Alkylation; D002219:Carbamates / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry*; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000737:chemistry
chemical_list: D000438:Alcohols; D002219:Carbamates; D014753:Vinyl Compounds; D002244:Carbon; D009584:Nitrogen