The Hydrogenation/Transfer Hydrogenation Network in Asymmetric Reduction of Ketones Catalyzed by [RuCl2(binap)(pica)] Complexes

阅读量:

56

作者:

C SandovalY LiK DingR Noyori

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摘要:

Chiral binap/pica-RuII complexes (binap=(S)- or (R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl; pica=-picolylamine) catalyze both asymmetric hydrogenation (AH) of ketones using H2 and asymmetric transfer hydrogenation (ATH) using non-tertiary alcohols under basic conditions. The AH and ATH catalytic cycles are linked by the metal–ligand bifunctional mechanism. Asymmetric reduction of pinacolone is best achieved in ethanol containing the Ru catalyst and base under an H2 atmosphere at ambient temperature, giving the chiral alcohol in 97–98 % ee. The reaction utilizes only H2 as a hydride source with alcohol acting as a proton source. On the other hand, asymmetric reduction of acetophenone is attained with both H2 (ambient temperature) and 2-propanol (>60 °C) with relatively low enant

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DOI:

10.1002/asia.200800246

被引量:

15

年份:

2008

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