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Studies on New Cross-Coupling Reactions : The Cleavage and Formation of C-C Bonds

新交叉偶联反应的研究: C-C 键的断裂和形成

基本信息

批准号：
18350053
负责人：
MIURA Masahiro
金额：
$ 9.52万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18350053/
关键词：
Synthetic Chemistry Cross-Couching Carbon Bond Transition Metal Catalyst π-Coniugated Molecules

项目摘要

Recently, effective carbon-carbonbond forming reactions have attracted much attention due to their utility for the synthesis of a variety of organic functional materials and biologically active agents. We have successfully developed a number of new catalytic coupling reactions of aromatic and unsaturated compounds which involve carbon-carbon and/or carbon-hydrogen bond cleavage and carbon-carbon bond formation. The purpose of this study is to improve their efficiency and selectivity and to develop other related new reactions. The catalytic reactions of aromatic substrates possessing carboxyl and bydroxyl groups with alkynes or alkenes were initially examined using various late transitionmetal catalysts. During the treatment of aromatic carboxylic acids with internal alkynes under rhodium catalysis, the oxidative 1:1 coupling efficiently proceeded via carbon-hydrogen bond cleavage to selectively give isocoumarin derivatives. On the other hand, in the reaction of same substrates under iridium catalysis, naphthalene derivatives were exclusively formed by the oxidative 1:2 coupling. The latter reaction appears to involve regioselective carbon-hydrogen bond cleavage directed by the carboxyl group and subsequent decarbaxylation. It was also found that the unique removable functional group can induce new coupling reactions around it. Thus, heteroaromatic carboxylic adds possessing indole and thiophene rings smoothly underwent the regioselective vinylation and mylation accompanied by decarboxylation under palladium catalysis. We also examined a number of other related couplings and succeeded to develop them. The results obtained through this study have been reported widely by academic papers and presentations in domestic and international conferences.

近年来，有效的碳-碳键形成反应由于其在合成各种有机功能材料和生物活性剂中的应用而引起了人们的广泛关注。我们已经成功地开发了一些新的芳香族和不饱和化合物的催化偶联反应，涉及碳-碳和/或碳-氢键断裂和碳-碳键形成。本研究的目的是提高它们的效率和选择性，并开发其他相关的新反应。用不同的后过渡金属催化剂对含羧基和羟基的芳香底物与炔或烯烃的催化反应进行了初步研究。在铑催化下，芳香羧酸与内炔的氧化1：1偶联通过碳-氢键断裂有效地进行，选择性地得到异香豆素衍生物。另一方面，在铱催化下的相同底物的反应中，萘衍生物仅通过氧化1：2偶联形成。后者的反应似乎涉及区域选择性的碳-氢键裂解的羧基基团和随后的脱羧。研究还发现，独特的可去除官能团可以在其周围诱导新的偶联反应，从而使含吲哚和噻吩环的杂芳羧酸在钯催化下顺利地进行了区域选择性的乙烯基化和甲基化反应，并伴随着脱羧反应。我们还研究了许多其他相关的耦合，并成功地开发了它们。本研究所取得的成果已被国内外学术论文和会议报告广泛报道。