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Development of novel double- and single carbonylation processes catalyzed by organotransition metal complexes

有机过渡金属配合物催化的新型双羰基化和单羰基化工艺的开发

基本信息

批准号：
08555231
负责人：
YAMAMOTO Akio
金额：
$ 9.79万
依托单位：
Waseda University.
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1998
项目状态：
已结题

项目摘要

We investigated here (I) the carbonylation processes of amitnes and alcohols catalyzed by palladium complexes and (2) C-O bond activation by palladium complexes and its application to novel catalytic hydrogenation processes.Major findings : (a) New direct carbonylation of benzyl alcohol catalyzed by a palladium complex with hydrogen iodide promoter to give phenylacetic acid in excellent yields in aqueous systems was discovered. Application of the carbonylation processes to other arylmethanol analogues provided convenient means to prepare 3-isochromanone, 1, 4-benzeneacetic acid, 2-hydroxybenzeneacetic acid, and 2-naphthaleneacetic acid.(b)Examination of the reactions of the (phenylacetyl)palladium complexes with secondary amines and alcohols provided supporting evidence for operation of different types of mechanisms for yielding amides and esters. The amide formation is proposed to proceed through coordination of the amine to the palladium center followed by its nucleophilic attack on the acyl group aided by a base. On the other hand, the formation of esters in reaction of acylpalladium with alcohols in the presence of a base is compatible with the reaction mechanism proceeding through an intermediate acyl-alkoxide complex.(c)Activation of C-O bonds in various oxygen-containing organic compounds such as carboxylic acid anhydrides, carboxylic esters, and diketene by palladium(O) complexes was found to lead to the corresponding products with C-O bond cleavage. Based on these findings, realization of halide-free aldehyde preparation processes by hydrogenation of anhydrides or direct hydrogenation of carboxylic acids in the presence of pivalic anhydride catalyzed by palladium complexes was achieved.

本文主要研究了钯配合物催化酰胺和醇的羰基化过程，钯配合物活化C-O键及其在新型催化加氢过程中的应用。主要发现：(a)发现了用钯配合物与碘化氢促进剂催化的苯甲醇直接羰基化反应，在水体系中得到收率极好的苯乙酸。羰基化工艺在其他芳基甲醇类似物上的应用为制备3-异氯罗曼酮、1,4 -苯乙酸、2-羟基苯乙酸和2-萘乙酸提供了方便的手段。(b)检查（苯乙酰基）钯配合物与仲胺和醇的反应，为不同类型的生产酰胺和酯的机制的操作提供了支持证据。酰胺的形成是通过胺与钯中心的配位进行的，然后在碱的帮助下对酰基进行亲核攻击。另一方面，在碱的存在下，酰基钯与醇的反应生成酯与中间酰基-醇盐络合物的反应机理是相容的。(c)发现钯(O)配合物对各种含氧有机化合物（如羧酸酸酐、羧酸酯和二烯酮）中的c -O键的活化可导致相应的c -O键裂解产物。在此基础上，通过酸酐加氢或在戊酸酐存在下钯配合物催化羧酸直接加氢，实现了无卤醛的制备工艺。