Enhanced hydrogenation activity and diastereomeric interactions of methyl pyruvate co-adsorbed with R-1-(1-naphthyl)ethylamine on Pd(111)

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

doi:10.1038/ncomms12380

Title: Enhanced hydrogenation activity and diastereomeric interactions of methyl pyruvate co-adsorbed with R-1-(1-naphthyl)ethylamine on Pd(111)

Journal Article · Thu Aug 04 00:00:00 EDT 2016 · Nature Communications

DOI:https://doi.org/10.1038/ncomms12380· OSTI ID:1326641

Mahapatra, Mausumi ^[1]; Burkholder, Luke ^[1];

^[2]; Bai, Yun ^[1]; Saldin, Dilano K. ^[1]; Tysoe, Wilfred T. ^[1]

Univ. of Wisconsin-Milwaukee, Milwaukee, WI (United States)
Univ. of Wisconsin-Milwaukee, Milwaukee, WI (United States); Univ. of Illinois at Urbana-Champaign, Champaign, IL (United States)

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. NEAþMP docking complexes are imaged using scanning tunneling 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. In conclusion, 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.

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Research Organization:: Univ. of Wisconsin, Milwaukee, WI (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-03ER15474; SC0008703

OSTI ID:: 1326641

Journal Information:: Nature Communications, Vol. 7; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 30 works

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