Direct experimental and computational evidence for the dihydride pathway in TangPHOS-Rh catalysed asymmetric hydrogenation

Ilya D. Gridnev; Christina Kohrt; Yuanyuan Liu

doi:10.1039/c3dt52383g

Direct experimental and computational evidence for the dihydride pathway in TangPHOS-Rh catalysed asymmetric hydrogenation

Ilya D. Gridnev^*
, Christina Kohrt
, Yuanyuan Liu

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

DFT computations of various possible reaction pathways in asymmetric hydrogenation of methyl (Z-α)acetylaminocinnamate catalysed by Rh-TangPHOS complex revealed the clear preference of the dihydride pathway. This conclusion was explicitly confirmed by the structure of the monohydride intermediate intercepted in the low temperature NMR hydrogenation experiments. DFT analysis of the origin of enantioselection showed that it takes place via obstructing the proper coordination of the double bond in the S-enantioselective pathway.

Original language	English
Pages (from-to)	1785-1790
Number of pages	6
Journal	Dalton Transactions
Volume	43
Issue number	4
DOIs	https://doi.org/10.1039/c3dt52383g
State	Published - 28 Jan 2014
Externally published	Yes

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abstract = "DFT computations of various possible reaction pathways in asymmetric hydrogenation of methyl (Z-α)acetylaminocinnamate catalysed by Rh-TangPHOS complex revealed the clear preference of the dihydride pathway. This conclusion was explicitly confirmed by the structure of the monohydride intermediate intercepted in the low temperature NMR hydrogenation experiments. DFT analysis of the origin of enantioselection showed that it takes place via obstructing the proper coordination of the double bond in the S-enantioselective pathway.",

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AU - Gridnev, Ilya D.

AU - Kohrt, Christina

AU - Liu, Yuanyuan

PY - 2014/1/28

Y1 - 2014/1/28

N2 - DFT computations of various possible reaction pathways in asymmetric hydrogenation of methyl (Z-α)acetylaminocinnamate catalysed by Rh-TangPHOS complex revealed the clear preference of the dihydride pathway. This conclusion was explicitly confirmed by the structure of the monohydride intermediate intercepted in the low temperature NMR hydrogenation experiments. DFT analysis of the origin of enantioselection showed that it takes place via obstructing the proper coordination of the double bond in the S-enantioselective pathway.

AB - DFT computations of various possible reaction pathways in asymmetric hydrogenation of methyl (Z-α)acetylaminocinnamate catalysed by Rh-TangPHOS complex revealed the clear preference of the dihydride pathway. This conclusion was explicitly confirmed by the structure of the monohydride intermediate intercepted in the low temperature NMR hydrogenation experiments. DFT analysis of the origin of enantioselection showed that it takes place via obstructing the proper coordination of the double bond in the S-enantioselective pathway.

UR - https://www.scopus.com/pages/publications/84890830716

U2 - 10.1039/c3dt52383g

DO - 10.1039/c3dt52383g

M3 - 文章

AN - SCOPUS:84890830716

SN - 1477-9226

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EP - 1790

JO - Dalton Transactions

JF - Dalton Transactions

IS - 4

ER -

Direct experimental and computational evidence for the dihydride pathway in TangPHOS-Rh catalysed asymmetric hydrogenation

Abstract

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