Takahashi Tamotsu, Li Yanzhong, Stepnicka Petr, Kitamura Masanori, Liu Yanjun, Nakajima Kiyohiko, Kotora Martin
Catalysis Research Center and Graduate School of Pharmaceutical Sciences, Hokkaido University, Japan.
J Am Chem Soc. 2002 Jan 30;124(4):576-82. doi: 10.1021/ja016848k.
Reactions of tetraiodobenzene with zirconacyclopentadienes, which were conveniently prepared from two alkynes (or diynes) and zirconocene complexes, afforded 1,2,3,4-tetrasubstituted diiodonaphthalene derivatives in good isolated yields. These 1,2,3,4-tetrasubstituted diiodonaphthalene derivatives could be converted to 1,2,3,4,5,6,7,8-octasubstituted anthracene derivatives by reaction with a second zirconacyclopentadiene. When the two zirconacyclopentadienes were different, unsymmetrical anthracenes such as 1,2,3,4-tetraethyl-5,6,7,8-tetraphenylanthracene (68% isolated yield) were obtained. On the other hand, treatment of a 2,3-dihalopyridine such as 2-bromo-3-iodopyridine with zirconacyclopentadienes gave 5,6,7,8-tetrasubstituted quinoline derivatives in good to high yields. 3,4-dihalopyridines such as 4-chloro-3-iodopyridine reacted with zirconacyclopentadienes to afford 5,6,7,8-tetrasubstituted isoquinoline derivatives in good to high yields.
四碘苯与锆环戊二烯的反应能方便地由两种炔烃（或二炔烃）和二茂锆配合物制备得到，以良好的分离产率得到1,2,3,4 - 四取代二碘萘衍生物。这些1,2,3,4 - 四取代二碘萘衍生物通过与第二种锆环戊二烯反应可转化为1,2,3,4,5,6,7,8 - 八取代蒽衍生物。当两种锆环戊二烯不同时，可得到不对称蒽，如1,2,3,4 - 四乙基 - 5,6,7,8 - 四苯基蒽（分离产率68%）。另一方面，用锆环戊二烯处理2,3 - 二卤代吡啶，如2 - 溴 - 3 - 碘吡啶，可得到产率良好至高的5,6,7,8 - 四取代喹啉衍生物。3,4 - 二卤代吡啶，如4 - 氯 - 3 - 碘吡啶，与锆环戊二烯反应，以良好至高的产率得到5,6,7,8 - 四取代异喹啉衍生物。
