Asymmetric hydrogenation of an α-unsaturated carboxylic acid catalyzed by intact chiral transition metal carbonyl cluster : diastereomeric control of enantioselectivity
Abstract
Twenty clusters of the general formula [(μ-H)2Ru3(μ3-S)(CO)7(μ-P–P*)] (P–P* = chiral diphosphine of the ferrocene-based Walphos or Josiphos families) have been synthesised and characterised. The clusters have been tested as catalysts for asymmetric hydrogenation of tiglic acid [trans-2-methyl-2-butenoic acid]. The observed enantioselectivities and conversion rates strongly support catalysis by intact Ru3 clusters. A catalytic mechanism involving an active Ru3 catalyst generated by CO loss from [(μ-H)2Ru3(μ3-S)(CO)7(μ-P–P*)] has been investigated by DFT calculations.
Main Authors
Format
Articles
Research article
Published
2020
Series
Subjects
Publication in research information system
Publisher
Royal Society of Chemistry
The permanent address of the publication
https://urn.fi/URN:NBN:fi:jyu-202012076940Käytä tätä linkitykseen.
Review status
Peer reviewed
ISSN
1477-9226
DOI
https://doi.org/10.1039/C9DT04799A
Language
English
Published in
Dalton Transactions
Citation
- Abdel-Magied, A. F., Theibich, Y., Singh, A. K., Rahaman, A., Doverbratt, I., Raha, A. K., Haukka, M., Richmond, M. G., & Nordlander, E. (2020). Asymmetric hydrogenation of an α-unsaturated carboxylic acid catalyzed by intact chiral transition metal carbonyl cluster : diastereomeric control of enantioselectivity. Dalton Transactions, 49(14), 4244-4256. https://doi.org/10.1039/C9DT04799A
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Additional information about funding
AFA thanks the EU Erasmus Mundus program for a predoctoral fellowship. AKS thanks the Carl Trygger Foundation for a postdoctoral fellowship. MGR thanks the Robert A. Welch Foundation (grant B-1093) for financial support and acknowledges computational resources through UNT’s High Performance Computing Services and CASCaM. We thank Dr David Hrovat and Prof. Xinzheng Yang for helpful ONIOMbased discussions. We are indebted to Dr Thomas Brimert at Red Glead Discovery for assistance with chiral HPLC measurements.
Copyright© The Royal Society of Chemistry 2020