Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 134, Issue 33, Pages 13624-13631Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja3018219
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- Oregon State University
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0848704] Funding Source: National Science Foundation
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Computational study of the mechanisms, and stereoselectivities of a dual amino catalyzed synthesis of Cyclohexenones containing all carbon gamma-quaternary and partial derivative-tertiary stereocenters is reported. Extensive conformational search with density functional theory optimizations, the high accuracy SCS-MP2/cc-pV infinity Z energies, and PCM solvation corrections were used to characterize all intermediates and transition states. Six mechanisms were considered, all consistent with available experiments. The reaction proceeds via sequential Michael and Mannich conjugate additions whereby the primary amine activates the aldehyde and the catalyst activates the pentenone. We have discovered a rare duumvirate stereocontrol: the Michael reaction sets the enantioselectivity, but both the Michael and the Mannich reactions control the diastereoselectivity.
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