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

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. 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...H 2N 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.

Authors:
 [1];  [1]; ORCiD logo [2];  [1];  [1];  [1]
  1. Univ. of Wisconsin-Milwaukee, Milwaukee, WI (United States)
  2. Univ. of Wisconsin-Milwaukee, Milwaukee, WI (United States); Univ. of Illinois at Urbana-Champaign, Champaign, IL (United States)
Publication Date:
Research Org.:
Univ. of Wisconsin, Milwaukee, WI (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1326641
Grant/Contract Number:  
FG02-03ER15474; SC0008703
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Mahapatra, Mausumi, Burkholder, Luke, Garvey, Michael, Bai, Yun, Saldin, Dilano K., and Tysoe, Wilfred T.. Enhanced hydrogenation activity and diastereomeric interactions of methyl pyruvate co-adsorbed with R-1-(1-naphthyl)ethylamine on Pd(111). United States: N. p., 2016. Web. doi:10.1038/ncomms12380.
Mahapatra, Mausumi, Burkholder, Luke, Garvey, Michael, Bai, Yun, Saldin, Dilano K., & Tysoe, Wilfred T.. Enhanced hydrogenation activity and diastereomeric interactions of methyl pyruvate co-adsorbed with R-1-(1-naphthyl)ethylamine on Pd(111). United States. doi:10.1038/ncomms12380.
Mahapatra, Mausumi, Burkholder, Luke, Garvey, Michael, Bai, Yun, Saldin, Dilano K., and Tysoe, Wilfred T.. Thu . "Enhanced hydrogenation activity and diastereomeric interactions of methyl pyruvate co-adsorbed with R-1-(1-naphthyl)ethylamine on Pd(111)". United States. doi:10.1038/ncomms12380. https://www.osti.gov/servlets/purl/1326641.
@article{osti_1326641,
title = {Enhanced hydrogenation activity and diastereomeric interactions of methyl pyruvate co-adsorbed with R-1-(1-naphthyl)ethylamine on Pd(111)},
author = {Mahapatra, Mausumi and Burkholder, Luke and Garvey, Michael and Bai, Yun and Saldin, Dilano K. and Tysoe, Wilfred T.},
abstractNote = {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.},
doi = {10.1038/ncomms12380},
journal = {Nature Communications},
number = ,
volume = 7,
place = {United States},
year = {Thu Aug 04 00:00:00 EDT 2016},
month = {Thu Aug 04 00:00:00 EDT 2016}
}

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Cited by: 7 works
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