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，我们开发了金属环和晚期过渡金属催化剂的不饱和有机化合物的新型合成方法。使用锆囊性周期性和镍复合物，发现并开发了苯和多环芳族化合物的催化合成方法。此外，开发了锆囊周期室与propgyl卤化物的反应的铜催化合成。它发现一系列的镍催化的环甲甲烷与烷烃与碱和碱的镍催化的环加成反应。在存在催化量的镍（II）氯化物BIS（三苯基膦）的情况下，锆囊性周期性二苯与2等于1-卤代或卤化卤化物的反应分别为相应的酸性烷基苯甲苯或戊二烯或pentasubSubSubSubSubStedenzene。这与与铜（i）氯化物作为催化剂的反应形成鲜明对比，该反应产生了相应的bis（Alkynyl）丁二烯。它是开发出来的是，氧化二氧化氢的偶联反应以及…更多1,2-二甲苯烯的偶联反应，介导或催化了镍化合物，可提供相应的多弹性配置混合物。通过由铜（i）氯化物介导的偶联反应的先例方法，适用的二核酸列被限制在二二菌或bromoiodoarenes中。然而，将铜（i）替换为镍（0）复合物，提高了锆对二溴苯基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。也就是说，在介绍了ni（cod）_2和20 mol％的pPh_3的10 mol％时，锆囊性周期性二烯与1,2-二甲苯的反应以良好的产率提供了相应的萘。研究了该方法用于各种锆囊性和二苯乙烯。在研究铜（I）盐的存在下，锆囊周期性苯甲酸的反应。在存在铜（I）氯化物的情况下，锆囊性周开甘油与两个等效的卤化物反应，使双甲基苯基化产物中等至高产率。通过控制CUCL的量，还可以逐步实现艾烯基化，并且还制备了多种未经对称的拨盘衍生物。较少的