钌催化碘代炔烃-环氧化合物官能团环化反应中的溶剂依赖性化学选择性
Solvent-dependent chemoselectivity in ruthenium-catalyzed cyclization of iodoalkyne-epoxide functionalities.
作者信息
Lin Ming-Yuan, Maddirala Shambabu Joseph, Liu Rai-Shung
机构信息
Department of Chemistry, National Tsing-Hua University, Hsinchu, Taiwan 30043, Republic of China.
出版信息
Org Lett. 2005 Apr 28;7(9):1745-8. doi: 10.1021/ol050317+.
[reaction: see text] Treatment of 1-(2'-iodoethynylphenyl)-2-propyloxirane (3) with TpRuPPh(3)(CH(3)CN)(2)PF(6) catalyst (10 mol %) produced 1-iodo-2-naphthol (3a) exclusively in DMF, but gave 2-iodobenzo[d]oxepin (3b) efficiently in benzene. Such a solvent-dependent chemoselectivity suggests a solution equilibrium between ruthenium-pi-iodoalkyne and ruthenium-2-iodovinylidene intermediates.
[反应：见正文] 用TpRuPPh(3)(CH(3)CN)(2)PF(6)催化剂（10摩尔%）处理1-(2'-碘乙炔基苯基)-2-丙基环氧乙烷（3），在N,N-二甲基甲酰胺中仅生成1-碘-2-萘酚（3a），但在苯中能高效生成2-碘苯并[d]氧杂环庚三烯（3b）。这种溶剂依赖性的化学选择性表明钌-π-碘炔和钌-2-碘亚乙烯基中间体之间存在溶液平衡。
Zotero 插件