Rhodium-Catalyzed Nitrene/Alkyne Metathesis: An Enantioselective Process for the Synthesis of N‑Heterocycles
Kemiao Hong†, Han Su†, Chao Pei†, Xinxin Lv‡, Wenhao Hu‡, Lihua Qiu*,†（邱丽华）, and Xinfang Xu*,†,‡ （徐新芳）
† College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
‡ Guangdong Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou, Guangdong 510006, China
Org. Lett.2019, 21, 3328--3331
A chiral dirhodium-carboxylates-catalyzed asymmetric nitrene/alkyne metathesis (NAM) cascade reaction of alkyne-tethered sulfamates has been developed, which provides a general access to the synthesis of tricyclic N-heterocycles in good yields and excellent enantioselectivity. The chiral dirhodium catalyst not only promotes the nitrene/alkyne metathesis (NAM) to generate the key α-imino metal carbene intermediate but also is responsible for the observed asymmetric induction in the terminating [2,3]-sigmatropic rearrangement of oxonium ylide species.