Enantiomeric products formed via different mechanisms: asymmetric hydrogenation of an α,β-unsaturated carboxylic acid involving a Ru(CH3COO)2[(R)-binap] catalyst |
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Authors: | Masahiro Yoshimura |
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Institution: | Research Center for Materials Science and the Department of Chemistry, Nagoya University, Chikusa, Nagoya 464-8602, Japan |
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Abstract: | Hydrogenation of (Z)-3-phenyl-2-butenoic acid with a Ru(CH3COO)2(R)-binap] (BINAP=2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) catalyst in methanol gives (S)-3-phenyl-2-butanoic acid and its R enantiomer in a 97:3 (4 atm) to 94:6 (100 atm) ratio in quantitative yield. Both hydrogen gas and protic methanol participate in the saturation of the olefinic bond. Analysis of the products obtained using (Z)-3-phenyl-2-butenoic acid-3-13C and either H2, a 1:1 H2-D2 mixture, or D2 in CH3OD indicates that several catalytic cycles are operative, showing different reactivity and stereoselectivity. The major S enantiomer was formed primarily by the standard Ru monohydride mechanism, whereas the minor R isomer is produced via more complicated routes. |
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Keywords: | Asymmetric hydrogenation BINAP-Ru α β-Unsaturated carboxylic acid Minor enantiomeric product Mechanism |
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