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Activation of allylic esters in an intramolecular vinylogous kinetic resolution reaction with synergistic magnesium catalysts.

ABSTRACT: Kinetic resolution (KR) of racemic starting materials is a powerful and practical alternative to prepare valuable enantiomerically enriched compounds. A magnesium-catalyzed kinetic resolution based on a designed intramolecular vinylogous Michael reaction is disclosed. Here we show a synergistic catalytic strategy based on the development of chiral ligands. Substrates containing linear allylic ester structures are designed and synthesized to construct key [6.6.5]-tricyclic chiral skeletons via this kinetic resolution process. Detailed mechanistic studies reveal a rational mechanism for the current intramolecular vinylogous KR reaction. The desired direct intramolecular asymmetric vinylogous Michael reaction of linear allylic esters is realized in high efficiency and enantioselectivity with the synergistic catalytic system.

SUBMITTER: Li D

PROVIDER: S-EPMC7244749 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

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Activation of allylic esters in an intramolecular vinylogous kinetic resolution reaction with synergistic magnesium catalysts.

Li Dan D Yang Yuling Y Zhang Minmin M Wang Linqing L Xu Yingfan Y Yang Dongxu D Wang Rui R

Nature communications 20200522 1

Kinetic resolution (KR) of racemic starting materials is a powerful and practical alternative to prepare valuable enantiomerically enriched compounds. A magnesium-catalyzed kinetic resolution based on a designed intramolecular vinylogous Michael reaction is disclosed. Here we show a synergistic catalytic strategy based on the development of chiral ligands. Substrates containing linear allylic ester structures are designed and synthesized to construct key [6.6.5]-tricyclic chiral skeletons via th ...[more]

PMID: 32444612

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