title: Rhodium-Catalyzed Enantioselective Cycloisomerization to Cyclohexenes Bearing Quaternary Carbon Centers.
abstract: We report a Rh-catalyzed enantioselective cycloisomerization of α,ω-heptadienes to afford cyclohexenes bearing quaternary carbon centers. Rhodium(I) and a new SDP ligand promote chemoselective formation of a cyclohex-3-enecarbaldehyde motif that is inaccessible by the Diels-Alder cycloaddition. Various α,α-bisallylaldehydes rearrange to generate six-membered rings by a mechanism triggered by aldehyde C-H bond activation. Mechanistic studies suggest a pathway involving regioselective carbometalation and endocyclic β-hydride elimination.
authors.affiliation: Department of Chemistry, University of California, Irvine , 4403 Natural Sciences 1, Irvine, California 92697, United States.
authors.forename: Jung-Woo
authors.initials: JW
authors.lastname: Park
authors.affiliation: Department of Chemistry, University of California, Irvine , 4403 Natural Sciences 1, Irvine, California 92697, United States.
authors.forename: Zhiwei
authors.initials: Z
authors.lastname: Chen
authors.affiliation: Department of Chemistry, University of California, Irvine , 4403 Natural Sciences 1, Irvine, California 92697, United States.
authors.forename: Vy M
authors.initials: VM
authors.lastname: Dong
mesh_terms: D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry; D000498:Allyl Compounds / Q000737:chemistry*; D003500:Cyclization; D053138:Cyclohexenes / Q000138:chemical synthesis*; D009285:Naphthoquinones / Q000138:chemical synthesis; D009942:Organometallic Compounds / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D000498:Allyl Compounds; D053138:Cyclohexenes; D009285:Naphthoquinones; D009942:Organometallic Compounds; C477934:pinnatal; D012238:Rhodium