Asymmetric hydrogenation of an α-unsaturated carboxylic acid catalyzed by intact chiral transition metal carbonyl clusters - diastereomeric control of enantioselectivity

Ahmed F Abdel-Magied; Yusuf Theibich; Amrendra K Singh; Ahibur Rahaman; Isa Doverbratt; Arun K Raha; Matti Haukka; Michael G Richmond; Ebbe Nordlander

doi:10.1039/c9dt04799a

Asymmetric hydrogenation of an α-unsaturated carboxylic acid catalyzed by intact chiral transition metal carbonyl clusters - diastereomeric control of enantioselectivity

Dalton Trans. 2020 Apr 7;49(14):4244-4256. doi: 10.1039/c9dt04799a.

Authors

Ahmed F Abdel-Magied¹, Yusuf Theibich¹, Amrendra K Singh¹, Ahibur Rahaman¹, Isa Doverbratt², Arun K Raha¹, Matti Haukka³, Michael G Richmond⁴, Ebbe Nordlander¹

Affiliations

¹ Chemical Physics, Department of Chemistry, Lund University, Box 124, SE-221 00, Lund, Sweden. Ebbe.Nordlander@chemphys.lu.se.
² Centre for Analysis and Synthesis, Department of Chemistry, Lund University, Box 124, SE-221 00, Lund, Sweden.
³ Department of Chemistry, University of Jyväskylä, Box 35, FI-400 14, Jyväskylä, Finland.
⁴ Department of Chemistry, The University of North Texas, Denton, Texas 76203, USA.

PMID: 32103214
DOI: 10.1039/c9dt04799a

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.