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

本论文研究了利用金属杂环化合物和后过渡金属催化剂合成不饱和有机化合物的新方法。利用锆环戊二烯和镍配合物，发现并发展了苯和多环芳香族化合物的催化合成方法。此外，还发展了铜催化的锆杂环戊烷与炔丙基卤反应合成二联烯的方法，发现了镍催化的锆杂环戊二烯与烯烃和炔的一系列环加成反应。在催化量的氯化镍（II）双（三苯基膦）存在下，锆环戊二烯与2当量的1-卤代炔或烯丙基卤反应，分别得到相应的炔基苯或五取代苯。这与用氯化铜（I）作为催化剂的反应形成鲜明对比，该反应产生相应的双（炔基）丁二烯。 关于我们 镍配合物介导或催化1，2-二卤代苯，得到相应的多环化合物。通过由氯化铜（I）介导的偶联反应的先前方法，适用的二卤代芳烃限于二碘代芳烃或溴代碘代芳烃。然而，将铜（I）取代为镍（0）络合物，提高了锆杂环对二溴-甚至二氯苯的反应性。此外，3-三氟甲基苯乙烯的使用改善了镍催化的反应。即在10mol%Ni（cod）_2和20mol%PPh_3存在下，锆环戊二烯与1，2-二卤代苯反应，以较好的产率得到相应的萘。研究了在铜盐存在下，锆杂环戊烷与炔丙基卤的反应。在氯化亚铜（I）存在下，锆杂环戊烷与两当量的炔丙基卤反应，以中等至高产率得到双丙二烯化产物。通过控制CuCl的用量，实现了联烯化反应的分步进行，并合成了一系列不对称取代的联烯衍生物。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