Bimetallic‐Catalyzed Reduction of Carboxylic Acids and Lactones to Alcohols and Diols

Bimetallic‐Catalyzed Reduction of Carboxylic Acids and Lactones to Alcohols and Diols
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DOI:
10.1002/1615-4169(200207)344:5
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发表时间:
2002-07
影响因子:
5.4
通讯作者:
A. Behr;Volker A. Brehme
A. Behr;Volker A. Brehme
中科院分区:
化学2区
文献类型:
--
作者:
A. Behr;Volker A. Brehme

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研究了均相催化氢还原羧酸的反应。由第8族或第9族后过渡金属和第二第6族或第7族过渡金属羰基组成的双金属催化剂显示出协同效应,允许在温和条件下以良好的产率转化。除了不同的催化剂前体的影响,温度,氢气压力,和催化剂浓度的影响进行了研究。[Rh(acac)(CO)2]和[Mo(CO)6]的等摩尔混合物显示出最高的活性,因此被应用于内酯到二醇的还原。发现催化剂的还原电位取决于所用内酯的环尺寸。五元环内酯几乎不转化为二醇,而六元和七元环内酯容易反应。
The homogeneously catalyzed reduction of carboxylic acids with hydrogen was studied. Bimetallic catalysts consisting of a group 8 or 9 late transition-metal and a second group 6 or 7 transition-metal carbonyl showed a synergistic effect allowing the conversion in good yields under moderate conditions. Besides the effect of different catalyst precursors, the influence of temperature, hydrogen pressure, and catalyst concentration was investigated. An equimolar mixture of [Rh(acac)(CO)2] and [Mo(CO)6] showed the highest activity and was therefore applied to the reduction of lactones to diols. The reduction potential of the catalyst was found to be dependent on the ring size of the lactone used. Five-membered ring lactones were hardly converted to diols whereas six- and seven- membered ring lactones reacted easily.