Enantioselective Synthesis of Tetrahydropyridines/Piperidines via Stepwise [4 + 2]/[2 + 2] Cyclizations
datasetposted on 2017-05-30, 21:29 authored by Zhen Wang, Huacheng Xu, Qin Su, Ping Hu, Pan-Lin Shao, Yun He, Yixin Lu
A phosphine-catalyzed novel enantioselective [4 + 2]-annulation reaction between allene ketones and 1-azadienes has been developed, and tetrahydropyridines were obtained in good yields and with excellent enantioselectivities. Subsequent exposure of tetrahydropyridines to benzyne leads to a [2 + 2]-cyclization, creating optically enriched polycyclic piperidines with a quaternary stereogenic center and a cyclobutene moiety. The reported stepwise [4 + 2]/[2 + 2]-cycloadditions represent a new approach to access enantiomerically enriched nitrogen-containing six-membered ring systems.
TetrahydropyridineCyclizationbenzynepolycyclic piperidines1- azadienescyclobutene moietyquaternary stereogenic centerenantioselectiveannulationcyclizationSubsequent exposurecycloadditionapproachnitrogen-containing six-membered ring systemsallene ketonesaccess enantiomericallyphosphine-catalyzedyieldtetrahydropyridineEnantioselective SynthesisenantioselectivitieStepwise