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晚期过渡金属催化剂合成不饱和有机化合物的新方法。以锆环戊二烯和镍为配合物，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，还研究了锆环戊烷与丙炔卤化物在铜催化下合成二烯的反应。发现了一系列镍催化的锆环戊二烯与烯烃和炔的环加成反应。在催化量的氯化二（三苯基膦）镍存在下，锆环戊二烯与2等量的1-卤代炔或烯丙基卤化物反应，分别生成相应的炔基苯或五取代苯。这与以氯化铜(I)为催化剂的反应形成鲜明对比，后者产生相应的二（炔基）丁二烯。在镍配合物的介导或催化下，锆环戊二烯与1,2-二卤苯的偶联反应得到了相应的多环化合物。用氯化铜(I)介导的偶联反应的方法，限制了二碘或溴碘芳烃的适用范围。然而，铜(I)被镍(0)络合物取代，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浓度为10mol %、PPh_3浓度为20mol %的条件下，锆环戊二烯与1,2-二卤苯的反应可以得到相应的萘。该方法适用于各种锆环戊二烯和二卤苯。研究了锆环戊烷与丙炔卤化物在铜(I)盐存在下的反应。在氯化铜(I)存在下，锆环戊烷与两种当量的丙炔卤化物反应，得到中高收率的双烯酰化产物。通过控制CuCl的用量，实现了逐步烯化反应，并制备了多种不对称取代的二烯衍生物。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