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使用 Rh/Ru 双金属催化剂或 Ru 单一组分催化剂将烯烃进行串联氢甲酰化/加氢反应制备正醇。

Tandem hydroformylation/hydrogenation of alkenes to normal alcohols using Rh/Ru dual catalyst or Ru single component catalyst.

机构信息

Department of Chemistry and Biotechnology, Graduate School of Engineering, University of Tokyo, Hongo, Bunkyo-ku, Japan.

出版信息

J Am Chem Soc. 2012 Nov 14;134(45):18746-57. doi: 10.1021/ja307998h. Epub 2012 Nov 1.

Abstract

The catalyst system for tandem hydroformylation/hydrogenation of terminal alkenes to the corresponding homologated normal alcohol was developed. The reaction mechanism for the Rh/Ru dual catalyst was investigated by real-time IR monitoring experiments and (31)P NMR spectroscopy, which proved the mutual orthogonality of Rh-catalyzed hydroformylation and Ru-catalyzed hydrogenation. Detailed investigation about Ru-catalyzed hydrogenation of undecanal under H(2)/CO pressure clarified different kinetics from the hydrogenation under H(2) and gave a clue to design more active hydrogenation catalysts under H(2)/CO atmosphere. The solely Ru-catalyzed normal selective hydroformylation/hydrogenation is also reported.

摘要

开发了用于末端烯烃的串联氢甲酰化/加氢反应的催化剂体系,以得到相应的同系化伯醇。通过实时红外监测实验和 (31)P NMR 光谱研究了 Rh/Ru 双催化剂的反应机理,证明了 Rh 催化的氢甲酰化和 Ru 催化的加氢反应的相互正交性。详细研究了在 H(2)/CO 压力下十一醛的 Ru 催化加氢反应,从 H(2)加氢反应中得到了不同的动力学,并为设计在 H(2)/CO 气氛下更具活性的加氢催化剂提供了线索。还报道了仅由 Ru 催化的伯醇选择性氢甲酰化/加氢反应。

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