State Key Laboratory of Elemento-Organic Chemsitry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University , Tianjin 300071, P. R. China.
Org Lett. 2016 Dec 2;18(23):6176-6179. doi: 10.1021/acs.orglett.6b03209. Epub 2016 Nov 18.
A method is developed for the synthesis of cyclopropanes from the C(sp)-C(sp) single bonds of β-keto esters with activated methylene compounds under metal-free conditions in the presence of 5-trimethylammonio-1,3-dioxo-1,3-dihydro-1λ-benzo[d][1,2]iodoxol-1-ol anion (AIBX), a recyclable water-soluble hypervalent iodine(V) reagent developed by our group. This mild, efficient method has a wide substrate scope and good functional group tolerance and is complementary to existing cyclopropanation strategies. The method can be used to construct polysubstituted ring-fused cyclopropanes and is amenable to further synthetic transformations for construction of complex biologically active molecules as well as asymmetric cyclopropanes (90% de) when a chiral ester auxiliary is used.
本文报道了一种在无金属条件下，通过三甲基铵-1,3-二氧代-1,3-二氢-1λ-苯并[d][1,2]碘代唑-1-醇阴离子（AIBX）的作用，利用β-酮酯与活性亚甲基化合物的 C(sp)-C(sp)单键，合成环丙烷的方法。AIBX 是我们小组开发的一种可回收的水溶性高价碘(V)试剂。该温和、高效的方法具有广泛的底物范围和良好的官能团容忍性，与现有的环丙烷化策略互补。该方法可用于构建多取代的稠环环丙烷，并且当使用手性酯辅助物时，还可进一步进行合成转化，构建复杂的生物活性分子以及不对称环丙烷（90%de）。
