Hu Linfeng, Li Jinzhao, Zhang Yongyan, Feng Xiaoming, Liu Xiaohua
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University Chengdu 610064 China
Chem Sci. 2022 Mar 11;13(14):4103-4108. doi: 10.1039/d2sc00419d. eCollection 2022 Apr 6.
An enantioselective [1,2] Stevens rearrangement was realized by using chiral guanidine and copper(i) complexes. Bis-sulfuration of α-diazocarbonyl compounds was developed through using thiosulfonates as the sulfenylating agent. It was undoubtedly an atom-economic process providing an efficient route to access novel chiral dithioketal derivatives, affording the corresponding products in good yields (up to 90% yield) and enantioselectivities (up to 96 : 4 er). A novel catalytic cycle was proposed to rationalize the reaction process and enantiocontrol.
通过使用手性胍和铜（I）配合物实现了对映选择性[1,2]史蒂文斯重排。以硫代磺酸酯作为亚磺酰化试剂，开发了α-重氮羰基化合物的双硫化反应。这无疑是一个原子经济的过程，为获得新型手性二硫代缩酮衍生物提供了一条有效途径，以良好的产率（高达90%）和对映选择性（高达96:4的对映体过量）得到相应产物。提出了一个新的催化循环来解释反应过程和对映体控制。
