title: Stereospecificity and stereoselectivity in electrophilic substitution reactions of non-alpha-heterosubstituted organolithiums and stannanes: a rotationally restricted amide as an internal stereochemical marker.
abstract: The complete stereochemical course of a tin-lithium exchange/electrophilic quench sequence has been unambiguously determined by stereochemical characterization (using X-ray crystallography or NOE studies) at every step. Pairs of diastereoisomeric stannanes of known stereochemistry bearing atropisomeric amide substituents undergo tin-lithium exchange with alkyllithiums to give diastereoisomeric benzylic organolithiums whose stereochemistry can be assigned by NMR. For one atropisomer of the stannanes, the tin-lithium exchange is fully stereospecific and proceeds with retention of stereochemistry. The other atropisomer undergoes nonstereospecific tin-lithium exchange: the first reported example of a lack of stereospecificity in electrophilic substitution of tin for lithium. One of the diastereoisomeric atropisomeric organolithiums produced by the tin-lithium exchange is deuterated and alkylated with retention but stannylated with inversion of stereochemistry. The other is alkylated nonstereospecifically but stannylated with retention.
authors.affiliation: Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
authors.forename: J
authors.initials: J
authors.lastname: Clayden
authors.forename: M
authors.initials: M
authors.lastname: Helliwell
authors.forename: J H
authors.initials: JH
authors.lastname: Pink
authors.forename: N
authors.initials: N
authors.lastname: Westlund