Hudlicky Tomas, Rinner Uwe, Finn Kevin J, Ghiviriga Ion
Department of Chemistry, Brock University, St. Catharines, Ontario, Canada L2S 3A1.
J Org Chem. 2005 Apr 29;70(9):3490-9. doi: 10.1021/jo040292c.
[reaction: see text] Indole and several indoles functionalized at C-2 were condensed with oxiranes, vinyloxiranes, aziridines, and vinylaziridines in the solid state on the surface of silica. The yields of these reactions were compared to those obtained from Lewis acid-catalyzed ring-opening reactions performed in solution and found to be superior in each case. The solid-phase aziridine opening constituted a key step in the synthesis of the beta-carbolin-1-one mimic of pancratistatin. Methyl 2-indolecarboxylate was found to react on the silica gel surface with N-tosylvinylaziridine in 68% yield. A nine-step synthesis of the pancratistatin mimic has been attained. The additional key transformation in this synthesis involved silica gel-catalyzed opening of an epoxide and hydrolysis of an acetonide. Detailed experimental procedures and full characterization are reported for all new compounds.
[反应：见正文] 吲哚及几种在C-2位官能化的吲哚与环氧乙烷、乙烯基环氧乙烷、氮丙啶和乙烯基氮丙啶在硅胶表面进行固态缩合反应。将这些反应的产率与在溶液中进行的路易斯酸催化的开环反应所获得的产率进行比较，发现每种情况下前者均更优。固相氮丙啶开环反应是合成泛喹酮β-咔啉-1-酮类似物的关键步骤。发现2-吲哚甲酸甲酯在硅胶表面与N-甲苯磺酰基乙烯基氮丙啶反应，产率为68%。已实现了泛喹酮类似物的九步合成。该合成中的另一个关键转化涉及硅胶催化的环氧化物开环和缩酮的水解。报道了所有新化合物的详细实验步骤和完整表征。
