title: Rhodium-catalyzed allylic substitution with an acyl anion equivalent: stereospecific construction of acyclic quaternary carbon stereogenic centers.
abstract: A highly regio- and stereospecific rhodium-catalyzed allylic alkylation of tertiary allylic alcohol derivatives with a cyanohydrin pronucleophile is described. This direct and operationally simple protocol provides a fundamentally novel approach toward the synthesis of α-quaternary substituted ketones and circumvents many of the inherent problems associated with conventional enolate alkylation reactions. The stereospecific variant of this reaction provides the enantiomerically enriched α-quaternary substituted allylic aryl ketone, which is a particularly challenging intermediate for more conventional enolate-based strategies.
authors.affiliation: Department of Chemistry, The University of Liverpool, Crown Street, Liverpool L69 7ZD, UK. andrew.evans@liverpool.ac.uk
authors.forename: P Andrew
authors.initials: PA
authors.lastname: Evans
authors.forename: Samuel
authors.initials: S
authors.lastname: Oliver
authors.forename: Jungha
authors.initials: J
authors.lastname: Chae
mesh_terms: D000838:Anions / Q000737:chemistry; D002384:Catalysis; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D020005:Propanols / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000838:Anions; D007659:Ketones; D009570:Nitriles; D009942:Organometallic Compounds; D020005:Propanols; C430593:cyanohydrin; C006463:allyl alcohol; D012238:Rhodium