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

在这项工作中，我们开发了利用金属环和后过渡金属催化剂合成不饱和有机化合物的新方法。以锆环戊二烯和镍配合物为原料，探索和发展了苯和多环芳香族化合物的催化合成方法。此外，还开发了铜催化的锆环戊烷与丙烯基卤化物的反应合成双烯丙烯的反应，发现镍催化的锆环戊二烯与烯烃和炔烃的一系列环加成反应。在催化量的氯化镍双(三苯基膦)存在下，锆环戊二烯与2当量的1-卤代炔或烯丙基卤化物反应，分别得到相应的炔基苯或五取代苯。这与以氯化铜为催化剂的反应生成相应的双(炔基)丁二烯的反应形成了鲜明的对比。发展了锆环戊二烯与…的偶联反应更多的1，2-二卤苯被镍配合物介导或催化合成相应的多环化合物。利用氯化铜催化偶联反应的前人方法，限制了二碘芳烃或溴碘芳烃的适用范围。然而，铜(I)取代镍(0)络合物，提高了锆环对二溴甚至二氯苯的反应活性。此外，3-(三氟甲基)苯乙烯的使用改善了镍催化的反应。也就是说，在Ni(CoD)_2和PPh_3的浓度分别为10%和20%的情况下，锆环戊二烯与1，2-二卤苯反应，以较高的产率得到相应的萘。将该方法应用于各种锆环戊二烯和二卤苯，考察了在铜(I)盐存在下，锆环戊烷与丙烯基卤化物的反应。在氯化铜(I)存在下，锆环戊烷与两个相当于丙烯基卤化物的化合物反应，以中等到高的产率得到双烯丙烯基化产物。通过控制CuCl量，实现了分步烯丙基化反应，合成了多种不对称取代的二烯丙烷衍生物。较少

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