Cobalt-Catalyzed Enantioselective Hydrogenation of Trisubstituted Carbocyclic Olefins: An Access to Chiral Cyclic Amides |
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| Authors: | Soumyadeep Chakrabortty Katharina Konieczny Felix J de Zwart Dr Eduard O Bobylev Dr Eszter Baráth Dr Sergey Tin Dr Bernd H Müller Prof?Dr Joost N H Reek Prof?Dr Bas de Bruin Prof?Dr Johannes G de Vries |
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| Institution: | 1. Leibniz Institute for Catalysis e.V. (LIKAT), Albert-Einstein-Strasse 29a, 18059 Rostock, Germany;2. Van't Hoff Institute for Molecular Sciences (HIMS), Science Park 904, 1098 XH Amsterdam, The Netherlands |
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| Abstract: | The enantioselective hydrogenation of cyclic enamides has been achieved using an earth-abundant cobalt-bisphosphine catalyst. Using CoCl2/(S,S)-Ph-BPE, several trisubstituted carbocyclic enamides were reduced with high activity and excellent enantioselectivity (up to 99 %) to the corresponding saturated amides. The methodology can be extended to the synthesis of chiral amines by base hydrolysis of the hydrogenation products. Preliminary mechanistic investigations reveal the presence of a high spin cobalt (II) species in the catalytic cycle. We propose that the hydrogenation of the carbon-carbon double bond proceeds via a sigma-bond-metathesis pathway. |
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| Keywords: | Chiral Phosphine Cobalt Enamide Homogeneous Catalysis Hydrogenation |
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