高碘酸钠氧化邻烷基羟基苯酚得到 6,6-螺-2,4-环己二烯酮化合物，接着自发通过Diels–Alder加成二聚的反应。此反应也被称为Adler-Singh反应。 反应机理 高碘酸钠通过与底物的酚羟基和烷基羟基配位后氧化，得到6,6-螺-2,4-环己二烯酮化合物，接着自身进行D-A加成反应得到产物。 反应实例
NaIO4 (47 g,0.22 mol) inwater (1 L)was addedtoa stirred solution of 2-hydroxybenzyl alcohol 1 (n = 1, 24.83 g, 0.2 mol) in water (1.5 L).After 10 min, colorless crystals appear.The mixture was kept for 24 h at 4 C in the dark. The crystalline product was filtered, washed (water) and dried in vacuum over P2O5 to afford 18.05 g of 3 (74%), mp 194–195 C. 【Adler E, Acta Chem Scand, 1971, 25, 2055】
【Castet F, Quideau S, Tetrahedron, 2007, 63, 6493】
【Singh V, Acc Chem Res, 1999, 32, 324】 |
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