Direct, stereoselective substitution in [Rh(CO)(2)Cl](2)-catalyzed allylic alkylations of unsymmetrical substrates.
[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]
Ashfeld
Brandon L
BL
Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, TX 78712, USA.
Miller
Kenneth A
KA
Martin
Stephen F
SF
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
D000498:Allyl Compounds; D002254:Carbonates; D002712:Chlorides; D012238:Rhodium