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Density functional study on enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine

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Abstract

The enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine is discussed by the density functional theory (DFT) method. The main intermediates and transition states for this reaction are optimized completely at the B3LYP/6-31g(d) level, and the transition states are verified by vibrational modes. As shown, the chirality-controlled steps for this reaction are the hydride transfer from borane to carbonyl carbon and oxime carbon of keto oxime ether, and the chirality for the reduced products is determined in these two reaction steps. In all examined reaction paths, the first hydride is transferred via a six-membered ring and the second hydride via a five-membered ring or a four-membered ring.

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Authors and Affiliations

  1. Department of Chemistry, Southwest-China Normal University, Chongqing, 400715, China

    Li Ming

  2. Department of Chemistry, Sichuan University, Chengdu, 610064, China

    Zheng Wenxu & Tian Anmin

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  1. Li Ming
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  2. Zheng Wenxu
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  3. Tian Anmin
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Correspondence to Li Ming.

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Li, M., Zheng, W. & Tian, A. Density functional study on enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine. SCI CHINA SER B 49, 296–307 (2006). https://doi.org/10.1007/s11426-006-2008-7

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  • DOI: https://doi.org/10.1007/s11426-006-2008-7

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