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Enhanced Hydrogenation Activity and Diastereomeric Interactions of Methyl Pyruvate Co-Adsorbed With R-1-(1-naphthyl)ethylamine on Pd(111)

Enhanced Hydrogenation Activity and Diastereomeric Interactions of Methyl Pyruvate Co-Adsorbed With R-1-(1-naphthyl)ethylamine on Pd(111)

Mausumi Mahapatra, Luke Burkholder, Michael Garvey, Yun Bai, Dilano K Saldin, Wilfred T Tysoe

Nat Commun. 2016 Aug 4;7:12380.

PMID: 27488075

Abstract:

Unmodified racemic sites on heterogeneous chiral catalysts reduce their overall enantioselectivity, but this effect is mitigated in the Orito reaction (methyl pyruvate (MP) hydrogenation to methyl lactate) by an increased hydrogenation reactivity. Here, this effect is explored on a R-1-(1-naphthyl)ethylamine (NEA)-modified Pd(111) model catalyst where temperature-programmed desorption experiments reveal that NEA accelerates the rates of both MP hydrogenation and H/D exchange. NEA+MP docking complexes are imaged using scanning tunnelling microscopy supplemented by density functional theory calculations to allow the most stable docking complexes to be identified. The results show that diastereomeric interactions between NEA and MP occur predominantly by binding of the C=C of the enol tautomer of MP to the surface, while simultaneously optimizing C=O····H2N hydrogen-bonding interactions. The combination of chiral-NEA driven diastereomeric docking with a tautomeric preference enhances the hydrogenation activity since C=C bonds hydrogenate more easily than C=O bonds thus providing a rationale for the catalytic observations.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP3886702	(R)-(+)-1-(1-Naphthyl)ethylamine		3886-70-2	Price

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