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Rhodium-Catalyzed Enantioselective Cycloisomerization to Cyclohexenes Bearing Quaternary Carbon Centers

Author:
Park, Jung-Woo, Chen, Zhiwei, Dong, Vy M.
Source:
Journal of the American Chemical Society 2016 v.138 no.10 pp. 3310-3313
ISSN:
1520-5126
Subject:
aldehydes, carbon, chemical bonding, cycloaddition reactions, cyclohexenes, enantiomers, ligands, rhodium
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.
Agid:
5418433