Isothiourea-catalyzed transfer hydrogenation of α,β-unsaturated para-nitrophenyl esters

Jiufeng Wu; Claire Mary Young; Andrew David Smith

doi:10.1016/j.tet.2020.131758

Isothiourea-catalyzed transfer hydrogenation of α,β-unsaturated para-nitrophenyl esters

Jiufeng Wu, Claire Mary Young, Andrew David Smith^*

^*Corresponding author for this work

School of Chemistry

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

Abstract

A protocol for the isothiourea-catalysed transfer hydrogenation of α,β-unsaturated para-nitrophenyl esters using Hantzsch ester has been developed. Good to excellent yields are observed using α,β-unsaturated aryl esters bearing electron-withdrawing β-substituents. The aryl ester products can either be isolated directly in moderate to excellent yields (7 examples, 16–98%) or converted to the corresponding methyl esters (2 examples, 68–70% yield) or benzyl amides (2 examples, 44–88% yield) after in situ reaction of the hydrogenated ester with the appropriate nucleophile. Preliminary experiments showed that modest enantioinduction (76:24 er) is possible when a chiral isothiourea catalyst was used.

Original language	English
Article number	131758
Journal	Tetrahedron
Volume	In press
Early online date	13 Nov 2020
DOIs	https://doi.org/10.1016/j.tet.2020.131758
Publication status	E-pub ahead of print - 13 Nov 2020

Keywords

Transfer hydrogenation
Isothiourea
Organocatalysis
Hantzsch ester

Access to Document

10.1016/j.tet.2020.131758

Wu_2020_Tetrahedron_Hydrogenation_AAM
Copyright © 2020 Elsevier Ltd. All rights reserved. This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1016/j.tet.2020.131758
Accepted author manuscript, 758 KBLicence: CC BY-NC-ND

RS Wolfson Merit Award: Developing Catalysis Research: New Reaction Discoveries and Practical Applications
Smith, A. D. (PI)
The Royal Society
1/01/15 → 31/12/19
Project: Fellowship
ERC Starting Grant EnolCat: Emulating nature: Reaction diversity and understanding through asymmetric catalysis
Smith, A. D. (PI)
European Commission
1/10/11 → 30/06/17
Project: Standard

data underpinning "Isothiourea-catalysed transfer hydrogenation of α,β-unsaturated para-nitrophenyl esters"
Smith, A. D. (Creator), Wu, J. (Creator) & Young, C. M. (Creator), University of St Andrews, 19 Nov 2020
DOI: 10.17630/b25b27ef-dca3-4590-b92d-221c243dde43
Dataset

File

Cite this

@article{4228e77eeaf94b768029105213e07699,

title = "Isothiourea-catalyzed transfer hydrogenation of α,β-unsaturated para-nitrophenyl esters",

abstract = "A protocol for the isothiourea-catalysed transfer hydrogenation of α,β-unsaturated para-nitrophenyl esters using Hantzsch ester has been developed. Good to excellent yields are observed using α,β-unsaturated aryl esters bearing electron-withdrawing β-substituents. The aryl ester products can either be isolated directly in moderate to excellent yields (7 examples, 16–98%) or converted to the corresponding methyl esters (2 examples, 68–70% yield) or benzyl amides (2 examples, 44–88% yield) after in situ reaction of the hydrogenated ester with the appropriate nucleophile. Preliminary experiments showed that modest enantioinduction (76:24 er) is possible when a chiral isothiourea catalyst was used.",

keywords = "Transfer hydrogenation, Isothiourea, Organocatalysis, Hantzsch ester",

author = "Jiufeng Wu and Young, {Claire Mary} and Smith, {Andrew David}",

note = "The research leading to these results (JW) has received funding from the ERC under the European Union's Seventh Framework Programme (FP7/2007–2013)/ERC grant agreement no 279850. ADS thanks the Royal Society for a Wolfson Research Merit Award. ",

year = "2020",

month = nov,

day = "13",

doi = "10.1016/j.tet.2020.131758",

language = "English",

volume = "In press",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier",

}

TY - JOUR

T1 - Isothiourea-catalyzed transfer hydrogenation of α,β-unsaturated para-nitrophenyl esters

AU - Wu, Jiufeng

AU - Young, Claire Mary

AU - Smith, Andrew David

N1 - The research leading to these results (JW) has received funding from the ERC under the European Union's Seventh Framework Programme (FP7/2007–2013)/ERC grant agreement no 279850. ADS thanks the Royal Society for a Wolfson Research Merit Award.

PY - 2020/11/13

Y1 - 2020/11/13

N2 - A protocol for the isothiourea-catalysed transfer hydrogenation of α,β-unsaturated para-nitrophenyl esters using Hantzsch ester has been developed. Good to excellent yields are observed using α,β-unsaturated aryl esters bearing electron-withdrawing β-substituents. The aryl ester products can either be isolated directly in moderate to excellent yields (7 examples, 16–98%) or converted to the corresponding methyl esters (2 examples, 68–70% yield) or benzyl amides (2 examples, 44–88% yield) after in situ reaction of the hydrogenated ester with the appropriate nucleophile. Preliminary experiments showed that modest enantioinduction (76:24 er) is possible when a chiral isothiourea catalyst was used.

AB - A protocol for the isothiourea-catalysed transfer hydrogenation of α,β-unsaturated para-nitrophenyl esters using Hantzsch ester has been developed. Good to excellent yields are observed using α,β-unsaturated aryl esters bearing electron-withdrawing β-substituents. The aryl ester products can either be isolated directly in moderate to excellent yields (7 examples, 16–98%) or converted to the corresponding methyl esters (2 examples, 68–70% yield) or benzyl amides (2 examples, 44–88% yield) after in situ reaction of the hydrogenated ester with the appropriate nucleophile. Preliminary experiments showed that modest enantioinduction (76:24 er) is possible when a chiral isothiourea catalyst was used.

KW - Transfer hydrogenation

KW - Isothiourea

KW - Organocatalysis

KW - Hantzsch ester

U2 - 10.1016/j.tet.2020.131758

DO - 10.1016/j.tet.2020.131758

M3 - Article

SN - 0040-4020

VL - In press

JO - Tetrahedron

JF - Tetrahedron

M1 - 131758

ER -

Isothiourea-catalyzed transfer hydrogenation of α,β-unsaturated para-nitrophenyl esters

Abstract

Keywords

Access to Document

Fingerprint

Projects

RS Wolfson Merit Award: Developing Catalysis Research: New Reaction Discoveries and Practical Applications

ERC Starting Grant EnolCat: Emulating nature: Reaction diversity and understanding through asymmetric catalysis

Datasets

data underpinning "Isothiourea-catalysed transfer hydrogenation of α,β-unsaturated para-nitrophenyl esters"

Cite this