Development of Novel Synthetic Methods by Cooperative Use of Metalacycles and Late Transition Metal Catalysts

金属环化合物和后过渡金属催化剂协同使用的新合成方法的开发

基本信息

批准号：
16550088
负责人：
TAKAHASHI Tamotsu
金额：
$ 2.43万
依托单位：
Hokkaido University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

项目摘要

In this work, we have developed novel synthetic methods of unsaturated organic compounds by metalacycles and late transition-metal catalysts. With zirconacyclopentadienes and nickel complexes, catalytic synthetic methods of benzene and polycyclic aromatic compounds were found and developed. Moreover, copper-catalyzed synthesis of diallenes from reactions of zirconacyclopentanes with propargyl halides was developed.It was found that a series of nickel-catalyzed cycloaddition reactions of zirconacyclopentadienes with alkenes and alkynes. In the presence of a catalytic amount of nickel(II) chloride bis(triphenylphosphine), a zirconacyclopentadiene reacted with 2 equiv of 1-haloalkyne or allyl halide to afford the corresponding alkynylbenzene or pentasubstituted benzene, respectively. This is striking contrast to the reaction with copper(I) chloride as a catalyst, which produced the corresponding bis(alkynyl)butadiene.It was developed that coupling reactions of zirconacyclopentadienes and … More 1,2-dihalobenzenens mediated or catalyzed by nickel complexes to afford the corresponding polycyclic compounds. By the precedent method of the coupling reaction which is mediated by copper(I) chloride, the applicable dihaloarenes were limited for the diiodo- or bromoiodoarenes. Substitution of copper(I) to nickel(0) complex, however, raised the reactivity of the zirconacycles toward dibromo- and even dichlorobenzenes. Furthermore, the use of 3-(trifluoromethyl)styrene improved the reaction for the nickel-catalyzed one. That is, in the presense of 10 mol% of Ni(cod)_2 and 20 mol% of PPh_3, the reaction of a zirconacyclopentadiene with 1,2-dihalobenzene afforded the corresponding naphthalene in a good yield. The method was applied for various zirconacyclopentadienes and dihalobenzenes.Reactions of zirconacyclopentanes with propargyl halides in the presence of copper(I) salt were investigated. In the presence of copper(I) chloride, zirconacyclopentanes reacted with two equivalents of a propargyl halide to give bisallenylation products in moderate to high yields. By controlling the amount of CuCl, stepwise allenylation was achieved and a variety of unsymmetrically substituted diallene derivatives were prepared as well. Less

在这项工作中，我们开发了用环戊二烯和镍配合物催化合成不饱和有机化合物的新方法，并发现并开发了铜催化合成苯和多环芳族化合物的方法。开发了由环戊烷锆与卤代炔烃反应生成的二烯。环戊二烯锆与烯烃和炔烃的环加成反应在催化量的氯化镍(II)双(三苯基膦)存在下，环戊二烯锆与2当量的1-卤代炔或烯丙基卤反应，分别得到相应的炔基苯或五取代苯。这与的反应形成鲜明对比。以氯化铜(I)为催化剂，生成相应的双(炔基)丁二烯。开发了锆环戊二烯与1,2-二卤代苯在镍配合物介导或催化下的偶联反应，得到相应的多环化合物。以前的由氯化铜(I)介导的偶联反应的方法，适用的二卤代芳烃仅限于二碘代或然而，用铜(I)取代镍(0)络合物提高了锆环对二溴苯甚至二氯苯的反应性。此外，使用3-(三氟甲基)苯乙烯改善了镍催化的反应。即，在10 mol%的Ni(cod)_2和20 mol%的PPh_3存在下，环戊二烯锆与 1,2-二卤代苯的反应以良好的收率得到了相应的萘。该方法适用于各种环戊二烯锆和二卤代苯。研究了环戊二烯锆与卤代丙烷在铜 (I) 盐存在下的反应。氯化铜(I)存在下，环戊烷与两种物质反应通过控制CuCl的用量，实现了逐步联烯基化，并制备了多种不对称取代的二烯基衍生物。