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Exploitation of New Synthetic Reactions via C-H Bond Activation by Transition Metal Catalysts

通过过渡金属催化剂活化 C-H 键开发新的合成反应

基本信息

批准号：
07455363
负责人：
FUJIWARA Yuzo
金额：
$ 4.74万
依托单位：
KYUSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

Our research on this project has discovered and developed the following two new synthetic reactions : 1) carboxylation of arenes with CO by palladium catalysts under very mild conditions, and 2) aminomethylation of alkanes with methyl-tert-amine N-oxides by copper catalysts.1. Carboxylation of Arenes with CO by Palladium Catalysts under Very Mild Conditions(1) The Pd (OAc)_2 catalyzed carboxylation reaction of aromatic compounds such as benzene, toluene, anisole, chlorobenzene, and naphthalene with CO in the presence of trifluoroacetic acid and K_2S_2O_8, to give the corresponding aromatic carboxylic acids in high yields under the vary mild conditions (1 atm CO,room temperature) has been discovered.(2) The reaction proceeds electrophilically with o, p-orientation when an electron-releasing group is attached to the benzene ring.2. Aminomethylation of Alkanes with Methyl-tert-amine N-oxides by Copper Catalysts(1) The Cu (OAc)_2/K_2S_2O_8/CF_3 COOH system has been found to cause the aminomethylation reaction of alkanes (10 atm) with methyl-tert-amine N-oxidess at 150ﾟC to give the corresponding amines in high yields.(2) Reactions of propane and ethane with trimetjylamine N-oxide gives N,N'-dimethylisobutylamine and N,N'-dimethylpropylamine, respectively. But methane remains unreacted under the present reaction conditions and the work is underway.

我们在本项目的研究中发现并发展了以下两个新的合成反应：1）芳烃与CO在钯催化剂作用下在非常温和的条件下的羧化反应; 2）烷烃与甲基叔胺N-氧化物在铜催化剂作用下的氨甲基化反应.钯催化芳烃与CO的温和羧化反应（1）在三氟乙酸和K_2S_2O_8存在下，Pd（OAc）_2催化苯、甲苯、苯甲醚、氯苯和萘等芳香族化合物与CO的羧化反应，在各种温和条件下高产率地得到相应的芳香族羧酸（1 atm CO，室温）。(2)当苯环上连接一个释放电子的基团时，反应以亲电的方式进行，具有o，p-取向.铜催化剂上烷烃与甲基叔胺N-氧化物的氨甲基化反应（1）在Cu（OAc）_2/K_2S_2O_8/CF_3COOH体系中，150 ℃下，烷烃（10个大气压）与甲基叔胺N-氧化物发生氨甲基化反应，高产率地得到相应的胺。(2)丙烷和乙烷与三甲基胺N-氧化物反应，分别得到N，N ′-二甲基异丁胺和N，N ′-二甲基丙胺。但是甲烷在目前的反应条件下仍然没有反应，这项工作正在进行中。