Asymmetric reactions. X. Asymmetric hydrogenation catalyzed by bis(dimethylglyoximato)cobalt(II)-chiral cocatalyst (amino alcohol) system.

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概要

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• The catalytic asymmetric hydrogenations of α-diketones, α-keto carboxylates, α-(acylamino)acrylates, α-phenylacrylophenone, and α-phenylacrylate were examined with bis(dimethylglyoximato)cobalt(II)–chiral cocatalyst (amino alcohol) and with simple achiral base coordinated bis(dimethylglyoximato)cobalt(II)–chiral cocatalyst (amino alcohol) systems. These gave corresponding optically active reduction products, and in some cases, optically active reductive dimerization products. High degrees of enantioselectivities (≈78%) are achieved in the hydrogenation of α-diketones. Evidence for non-binding of chiral base to cobalt complexes was presented in the case of latter system, <I>i.e.</I>, it was shown that the catalytic site and the enantioselectivity-determining site are separated in this system, as in enzymes. The importance of protonated chiral bases for enantioselection was also shown. Based on these results and the stereochemical correlations between structures of the chiral bases and those of the products, a mechanism for this asymmetric hydrogenation was proposed.

• 公益社団法人 日本化学会の論文

著者

• Takeuchi Seiji

  Niigata College Of Pharmacy

• OHGO Yoshiaki

  Niigata College of Pharmacy

• Yoshimura Juji

  Laboratorium für Organische Chemie Technische Hochschule Tokyo

• Natori Yukikazu

  Niigata College of Pharmacy

関連論文

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• Chiral Lattice-Controlled Asymmetric Photoisomerization of (2-Cyanoethyl)cobaloximes in the Solid State
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• The SmI_2 Mediated Cross-Coupling Reaction of Aldehydes with α-Diketones in Their Aqueous Forms
• Asymmetric Synthesis of Ketones by SmI_2-Mediated Allylation or Benzylation of Ketenes Followed by Enantioselective Protonation
• Crystalline-State Reaction of Cobaloxime Complexes. 18. Metastable Intermediate Structure Observed by a New X-Ray Diffractometer for Rapid Data Collection
• Reactions in Solid and Constrained State. IV.^ Preparation and Solid-State Photoracemization of Optically Active Alkyl Cobaloxime Complexes
• β-α Photoisomerization of Cobaloxime Complexes in the Solid State. 5.^ Reaction Rate Reduced by a Hydrogen Bond
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