title: Regio- and enantiospecific rhodium-catalyzed allylic substitution with an acyl anion equivalent.
abstract: The construction of enantiomerically enriched acyclic quaternary substituted ketones via the regio- and enantiospecific rhodium-catalyzed allylic alkylation reaction of chiral nonracemic tertiary alcohols with cyanohydrin pronucleophiles is described. This approach provides an alternative method to the α-arylation and vinylation of acyclic disubstituted ketone enolates, which remains a challenging endeavor. The combination of the allylic alkylation with ring-closing metathesis facilitates the preparation of enantiomerically enriched 2,2-disubstituted naphthalene-1-ones, which have proven very difficult to prepare using a more conventional dearomatization strategy.
authors.affiliation: Department of Chemistry, Queen's University , 90 Bader Lane, Kingston, ON, K7L 3N6, Canada , and Department of Chemistry, University of Liverpool , Crown Street, Liverpool L69 7ZD, United Kingdom.
authors.forename: P Andrew
authors.initials: PA
authors.lastname: Evans
authors.forename: Samuel
authors.initials: S
authors.lastname: Oliver
mesh_terms: D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D000838:Anions / Q000737:chemistry*; D002384:Catalysis; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009281:Naphthalenes / Q000138:chemical synthesis* / Q000737:chemistry; D012238:Rhodium; D013237:Stereoisomerism
chemical_list: D000498:Allyl Compounds; D000838:Anions; D007659:Ketones; D009281:Naphthalenes; D012238:Rhodium