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】

相关文献

1 Adler E,  Acta Chem Scand, 1959, 13 505

2 Adler E,  Acta Chem Scand, 1960, 14 1261, 1580

3 Adler E,  Acta Chem Scand, 1962, 16 529

4 Adler E,  Acta Chem Scand, 1971, 25 2055

5 Singh V,  J Chem Soc Chem Comm, 1992, 1212

6 Waldmann H, Tet Lett, 1996, 37, 3833

7 Singh V, Acc Chem Res, 1999, 32, 324

8 Castet F, Quideau S,  Tetrahedron, 2007, 63, 6493

9 Singh V,  Org Biomol Chem,  2010, 8 ,4472