biostudies-literaturePark JWNIGMS NIH HHS3310-3https://www.ebi.ac.uk/biostudies/studies/S-EPMC4856524biostudies-literatureUnknown138(10)We report a Rh-catalyzed enantioselective cycloisomerization of ?,?-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 ?,?-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 ?-hydride elimination.Journal of the American Chemical SocietyRhodium-Catalyzed Enantioselective Cycloisomerization to Cyclohexenes Bearing Quaternary Carbon Centers.PMC4856524GM105938R01 GM105938Park JWChen ZDong VMfalseRhodium-Catalyzed Enantioselective Cycloisomerization to Cyclohexenes Bearing Quaternary Carbon Centers.We report a Rh-catalyzed enantioselective cycloisomerization of ?,?-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 ?,?-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 ?-hydride elimination.2016-01-01T00:00:00Z2016 Mar2020-10-31T08:24:27Z2019-03-27T02:13:02ZS-EPMC48565242695364010.1021/jacs.6b01445