Torrent Anna, González Iván, Pla-Quintana Anna, Roglans Anna, Moreno-Mañas Marcial, Parella Teodor, Benet-Buchholz Jordi
Department of Chemistry, Universitat de Girona, Campus de Montilivi, s/n. E-17071-Girona, Spain.
J Org Chem. 2005 Mar 18;70(6):2033-41. doi: 10.1021/jo048056p.
[reaction: see text] Nitrogen-containing 15-membered triacetylenic macrocycles known as 1,6,11-tris(arylsulfonyl)-1,6,11-triazacyclopentadeca-3,8,13-triynes (1) and enediynic macrocycles called 1,6,11-tris(arylsulfonyl)-1,6,11-triazacyclopentadeca-3-ene-8,13-diynes (4 and 5) were satisfactorily prepared. [2+2+2] cycloisomerization processes catalyzed by transition metals were tested in the above-mentioned macrocycles. Readily available and familiar cyclotrimerization precatalysts were examined for efficiency. Among them, the RhCl(CO)(PPh(3))(2) complex was found to catalyze the cycloisomerization reaction giving the desired cycloadducts in high yields.
[反应：见正文] 成功制备了含氮的15元三乙炔大环化合物，即1,6,11-三（芳基磺酰基）-1,6,11-三氮杂环十五碳-3,8,13-三炔（1）以及烯二炔大环化合物，即1,6,11-三（芳基磺酰基）-1,6,11-三氮杂环十五碳-3-烯-8,13-二炔（4和5）。在上述大环化合物中测试了过渡金属催化的[2 + 2 + 2]环异构化过程。对易于获得且熟悉的环三聚预催化剂的效率进行了考察。其中，发现RhCl(CO)(PPh(3))(2)配合物能催化环异构化反应，以高收率得到所需的环加合物。
