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Computational Prediction of Chiral Iron Complexes for Asymmetric Transfer Hydrogenation of Pyruvic Acid to Lactic Acid.

ABSTRACT: Density functional theory calculations reveal a formic acid-assisted proton transfer mechanism for asymmetric transfer hydrogenation of pyruvic acid catalyzed by a chiral Fe complex, FeH[(R,R)-BESNCH(Ph)CH(Ph)NH₂](?⁶-p-cymene), with formic acid as the hydrogen provider. The rate-determining step is the hydride transfer from formate anion to Fe for the formation and dissociation of CO₂ with a total free energy barrier of 28.0 kcal mol^-1. A series of new bifunctional iron complexes with ?⁶-p-cymene replaced by different arene and sulfonyl groups were built and computationally screened as potential catalysts. Among the proposed complexes, we found 1_g with ?⁶-p-cymene replaced by 4-isopropyl biphenyl had the lowest free energy barrier of 26.2 kcal mol^-1 and excellent chiral selectivity of 98.5% ee.

SUBMITTER: Wang W

PROVIDER: S-EPMC7221593 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature

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Computational Prediction of Chiral Iron Complexes for Asymmetric Transfer Hydrogenation of Pyruvic Acid to Lactic Acid.

Wang Wan W Yang Xinzheng X

Molecules (Basel, Switzerland) 20200420 8

Density functional theory calculations reveal a formic acid-assisted proton transfer mechanism for asymmetric transfer hydrogenation of pyruvic acid catalyzed by a chiral Fe complex, FeH[(R,R)-BESNCH(Ph)CH(Ph)NH2](η6-p-cymene), with formic acid as the hydrogen provider. The rate-determining step is the hydride transfer from formate anion to Fe for the formation and dissociation of CO2 with a total free energy barrier of 28.0 kcal mol<s ...[more]

PMID: 32325984

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