Organic azides play important roles in synthetic chemistry, chemical biology, drug discovery, and material science. Azido-functionalization of alkenes is one of the most efficient procedures for rapid introduction of azide group into organic compounds. But only a few examples have been documented in the catalytic asymmetric version of the azidation of alkenes. Herein, we report an unprecedented highly diastereo- and enantioselective bromoazidation of α,β-unsaturated ketones catalyzed by chiral N,N′-dioxide/Fe(OTf)₂ complexes. An array of aryl, heteroaryl, and alkyl substituted α,β-unsaturated ketones were transformed to the corresponding α-bromo-β-azido ketones in high yields with excellent diastereo- and enantioselectivities. The catalytic system was also applicable for chloroazidation and iodoazidation of chalcone. Kinetic studies and some control experiments suggested that the reaction might proceed via a 1,4-addition/halogenation pathway.

中文翻译：

---

铁催化的α，β-不饱和酮的不对称卤代叠氮化：具有两个邻位立体中心的有机叠氮化物的构建

有机叠氮化物在合成化学，化学生物学，药物发现和材料科学中起着重要作用。烯烃的叠氮基官能化是将叠氮化物基团快速引入有机化合物的最有效方法之一。但是，烯烃催化的不对称形式仅记录了几个例子。本文中，我们报道了空手性N，N'-二氧化物/ Fe（OTf）₂催化的α，β-不饱和酮的高度非对映异构和对映选择性溴叠氮化。复合体。将一系列芳基，杂芳基和烷基取代的α，β-不饱和酮高产率地转化为相应的α-溴-β-叠氮基酮，具有出色的非对映选择性和对映选择性。该催化体系也适用于查尔酮的氯代叠氮化和碘代叠氮化。动力学研究和一些对照实验表明，该反应可能通过1，4-加成/卤化途径进行。