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以重氮化合物和烯丙基硫醚/炔丙基硫醚为反应底物,通过手性辅基和大位阻配体的不对称双诱导策略,高对映选择性地实现了经由铜卡宾产生硫叶立德的不对称[2,3]-σ重排反应(Doyle-Kirmse反应).脱除手性辅基后反应最高可以得到96%ee对映选择性.机理探究实验表明,反应很可能经历了自由的叶立德重排过程.该反应被进一步应用到含手性中心烯丙基硫醚的动力学拆分中.
Diazonium compounds and allyl sulfide / propargyl sulfide as the reaction substrate, through asymmetric double-chiral auxiliaries and ligands double induction strategy, high enantioselective achieved through the copper carbene Resulting in the asymmetric [2,3] -σ rearrangement reaction (Doyle-Kirmse reaction) of sulfur ylide. The maximum 96% ee enantioselectivity was obtained after the chiral prosthetic group was removed. The mechanism of the experiment showed that the reaction was very likely Underwent the free Yelizhe rearrangement process.The reaction was further applied to the kinetic resolution of allyl sulfide containing chiral center.