TBHP氧化烯丙位sp^(3) C-H键制备其官能团化衍生物

Allylic alkylation via the cross-dehydrogenative-coupling reaction using TBHP as oxidant between Allylic sp^(3) C-H and methylenic sp^(3) C-H bonds

目的本文研究以TBHP(70%水溶液)氧化烯丙位sp^(3) C-H键,过渡金属催化实现其C-C官能团化,并成功合成一系列衍生物。方法以0.25倍当量的CuCl、0.1倍当量的CoCl2为催化剂,乙腈为溶剂,2倍当量TBHP为氧化剂,1.5倍当量分子筛为添加剂,在80℃反应条件下,可以有效地促进环己烯烯丙位C—H键的活化进而完成与乙酰丙酮的交叉脱氢偶联(CDC)反应。结果该体系也适用于其他与环己烯结构相似的环状烯烃烯丙位C-H键的官能团化反应,产率在60%~88%。结论该反应具有经济、条件温和等优点。

Objective In this paper,catalytic allylic C-C alkylation was developed via the oxidizing reaction of allylic sp^(3) C-H catalyzed by transition metals in the presence of an oxidizing reagent,TBHP in water(70%).Methods The cross-dehydrogenative-coupling(CDC)reaction of cyclohexene and acetylacetone worked well in acetonitrile at 80℃in presence of 0.25 equiv CuCl,0.1 equiv CoCl2 as catalysts,2.0 equiv THBP in water as oxidant,1.5 equiv molecular sieve as additive.Results The practical method was applicable to a range of cyclic olefins and gave a series of allylic C-H alkylation derivatives from 60%to 88%yields.Conclusion The reaction has the advantages of inexpensive and mild reaction conditions.