Mechanism of the Asymmetric Hydrogenation of Exocyclic α,β‐Unsaturated Carbonyl Compounds with an Iridium/BiphPhox Catalyst: NMR and DFT Studies |
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| Authors: | Yuanyuan Liu Prof. Ilya D. Gridnev Prof. Wanbin Zhang |
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| Affiliation: | 1. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China) http://wanbin.sjtu.edu.cn;2. Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki 3‐6, Aoba‐ku, Sendai 9808578 (Japan) |
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| Abstract: | The mechanism of the asymmetric hydrogenation of exocyclic α,β‐unsaturated carbonyl compounds with the (aS)‐Ir/iPr‐BiphPhox catalyst was studied by NMR experiments and DFT computational analyses. Computed optical yields of the asymmetric hydrogenation proceeding by an iridium(I)/iridium(III) mechanism involving a transition state stabilized through two intramolecular hydrogen bonds are in good accordance with the experimental ee values. |
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| Keywords: | density functional calculations hydrogenation iridium NMR spectroscopy reaction mechanisms |
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