Rh-catalyzed intramolecular olefin hydroacylation: enantioselective synthesis of seven- and eight-membered heterocycles.
This communication describes the first rhodium-catalyzed intramolecular olefin hydroacylation to produce medium-sized heterocyclic ketones with high regio- and enantiocontrol. Both alpha- and beta-substituted ketones can be produced, depending on catalyst choice and substrate structure. In this stereoselective C-H bond functionalization, ethers, sulfides, and sulfoxides function as effective directing groups. Results from an isotopic labeling study suggest reductive elimination is not the turnover-limiting step in this olefin hydroacylation; thus, the proposed mechanism is distinct from those previously reported.
Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada.
Matthew M
MM
Coulter
Peter K
PK
Dornan
Vy M
VM
Dong
D000215:Acylation; D000447:Aldehydes / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry*; D001547:Benzaldehydes / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D006571:Heterocyclic Compounds / Q000138:chemical synthesis*; D007659:Ketones / Q000138:chemical synthesis; D012238:Rhodium / Q000737:chemistry; D013237:Stereoisomerism
D000447:Aldehydes; D000475:Alkenes; D001547:Benzaldehydes; D006571:Heterocyclic Compounds; D007659:Ketones; D012238:Rhodium