Abstract
Inspired by the active site structures of lactate racemase and recently reported sulphur–carbon–sulphur (SCS) nickel pincer complexes, a series of scorpion-like SCS nickel pincer complexes with an imidazole tail and asymmetric claws was proposed and examined computationally as potential catalysts for the asymmetric transfer hydrogenation of 1-acetonaphthone. Density functional theory calculations reveal a proton-coupled hydride transfer mechanism for the dehydrogenation of (R)-(+)-1-phenyl-ethanol and the hydrogenation of 1-acetonaphthone to produce (R)-(+)-1-(2-naphthyl)ethanol and (S)-(−)-1-(2-naphthyl)ethanol. Among all proposed Ni complexes, 1Ph is the most active one with a rather low free energy barrier of 24 kcal/mol and high enantioselectivity of near 99% enantiomeric excess (ee) for the hydrogenation of prochiral ketones to chiral alcohols.
Highlights
The synthesis of chiral compounds by metal-catalyzed asymmetric hydrogenation reactions has been widely used in the pharmaceutical [1], agrochemical [2], fragrance [3], and other fine chemical industries [4]
Inspired by the structures of the active site of lactate racemase [17] and experimentally reported reported sulphur–carbon–sulphur (SCS) palladium pincer complexes [18], we recently proposed a sulphur–carbon–sulphur (SCS) palladium pincer complexes [18], we recently proposed a series of series of scorpion-like SCS nickel pincer complexes with an imidazole tail as potential catalysts for scorpion-like SCS nickel pincer complexes with an imidazole tail as potential catalysts for lactate lactate racemization [19]
Our density functional theory (DFT) calculations revealed a weak enantioselectivity enantioselectivity in the hydrogenation of pyruvate catalyzed by those SCS nickel pincer complexes in the hydrogenation of pyruvate catalyzed by those SCS nickel pincer complexes with unsymmetrical with unsymmetrical ligands
Summary
The synthesis of chiral compounds by metal-catalyzed asymmetric hydrogenation reactions has been widely used in the pharmaceutical [1], agrochemical [2], fragrance [3], and other fine chemical industries [4]. The catalytic asymmetric reduction of prochiral ketones and imines, especially asymmetric hydrogenation (AH) and asymmetric transfer hydrogenation (ATH), is one of the most efficient and versatile tools to produce chiral alcohols and amines In both academic and industrial operations, catalysts used for AH and ATH are typically based on noble metals, such as. Our density functional theory (DFT) calculations revealed a weak enantioselectivity enantioselectivity in the hydrogenation of pyruvate catalyzed by those SCS nickel pincer complexes in the hydrogenation of pyruvate catalyzed by those SCS nickel pincer complexes with unsymmetrical with unsymmetrical ligands. Based on those findings, we proposed and computationally examined ligands.
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