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Lavoie S, Laliberté MA, McBreen PH. Adsorption states and modifier-substrate interactions on Pt(111) relevant to the enantioselective hydrogenation of alkyl pyruvates in the Orito reaction. J Am Chem Soc. 2003;125(51):15756-7doi: 10.1021/ja036700w.
Lavoie, S., Laliberté, M. A., & McBreen, P. H. (2003). Adsorption states and modifier-substrate interactions on Pt(111) relevant to the enantioselective hydrogenation of alkyl pyruvates in the Orito reaction. Journal of the American Chemical Society, 125(51), 15756-7. https://doi.org/10.1021/ja036700w
Lavoie, S, et al. "Adsorption states and modifier-substrate interactions on Pt(111) relevant to the enantioselective hydrogenation of alkyl pyruvates in the Orito reaction." Journal of the American Chemical Society vol. 125,51 (2003): 15756-7. doi: https://doi.org/10.1021/ja036700w
Lavoie S, Laliberté MA, McBreen PH. Adsorption states and modifier-substrate interactions on Pt(111) relevant to the enantioselective hydrogenation of alkyl pyruvates in the Orito reaction. J Am Chem Soc. 2003 Dec 24;125(51):15756-7. doi: 10.1021/ja036700w. PMID: 14677961.
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J Am Chem Soc. 2003 Dec 24;125(51):15756-7. doi: 10.1021/ja036700w.

Adsorption states and modifier-substrate interactions on Pt(111) relevant to the enantioselective hydrogenation of alkyl pyruvates in the Orito reaction.

Journal of the American Chemical Society

S Lavoie, M-A Laliberté, P H McBreen

Affiliations

  1. Département de Chimie, Université Laval, Québec, Canada G1K 7P4.

PMID: 14677961 DOI: 10.1021/ja036700w

Abstract

Reflectance FTIR spectroscopy (RAIRS) was used to study the chemisorption and intermolecular interactions of methyl pyruvate and (+/-)-1-(1-naphthyl)ethylamine (NEA) on Pt(111). NEA serves, in this study, as a tractable model of a chiral modifier in the asymmetric hydrogenation of alpha-dicarbonyls on alkaloid-modified platinum surfaces-the Orito reaction. The results show the presence of a majority enediolate state on the clean surface. A perpendicularly adsorbed trans conformation state is populated at close to full-monolayer coverage on the clean surface. The latter state desorbs at 185 K. The enediolate undergoes dissociation at 230 K. NEA displays hydrogen-bond association at high coverages. Coadsorption studies show that NEA inhibits the formation of the enediolate state. Multilayer methyl pyruvate shows a clear hydrogen-bond interaction with chemisorbed NEA, leading to a reorientation of the ethylamine group. The high-coverage trans-chemisorbed methyl pyruvate state also hydrogen-bonds to chemisorbed NEA. The latter interaction renders the trans state stable to above 300 K. A new schematic mechanism for the Orito reaction is proposed on the basis of these data.

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