title: Catalytic enantioselective synthesis of atropisomeric biaryls: a cation-directed nucleophilic aromatic substitution reaction.
abstract: A catalytic enantioselective nucleophilic aromatic substitution reaction which yields axially chiral biaryl derivatives in excellent yields with e.r. values of up to 97:3 has been developed. This process uses a chiral counterion to direct the addition of thiophenolate to a prochiral dichloropyrimidine by a tandem desymmetrization/kinetic resolution mechanism. The products can be derivatized to a range of atropisomeric structures without any reduction in enantioenrichment, thus offering access to unexplored chiral biaryl architectures.
authors.affiliation: Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA (UK) http://msmith.chem.ox.ac.uk/
authors.forename: Roly J
authors.initials: RJ
authors.lastname: Armstrong
authors.forename: Martin D
authors.initials: MD
authors.lastname: Smith
mesh_terms: D001713:Biphenyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D001713:Biphenyl Compounds
keywords: aromatic substitution; atropisomerism; chirality; kinetic resolution; phase-transfer catalysis