title: Direct, stereoselective substitution in [Rh(CO)(2)Cl](2)-catalyzed allylic alkylations of unsymmetrical substrates.
abstract: [Rh(CO)(2)Cl](2) has been found to possess the unusual property of catalyzing allylic alkylations of unsymmetrical allylic carbonates with high levels of regioselectivity to provide products arising from substitution at the carbon atom bearing the leaving group, irrespective of the structure of the starting carbonate. The substitution reaction occurs with retention of stereochemistry at the reacting center, and the carbon-carbon double-bond stereochemistry of primary (Z)-allylic carbonates is maintained. [reaction: see text]
authors.affiliation: Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, TX 78712, USA.
authors.forename: Brandon L
authors.initials: BL
authors.lastname: Ashfeld
authors.forename: Kenneth A
authors.initials: KA
authors.lastname: Miller
authors.forename: Stephen F
authors.initials: SF
authors.lastname: Martin
mesh_terms: D000478:Alkylation; D000498:Allyl Compounds / Q000737:chemistry*; D002254:Carbonates / Q000737:chemistry; D002384:Catalysis; D002712:Chlorides / Q000737:chemistry*; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000498:Allyl Compounds; D002254:Carbonates; D002712:Chlorides; D012238:Rhodium