Qin Hong, Chen Feng, Du Jinze, Yang Xiaobing, Huang Yiping, Zhu Kai, Yue Changhai, Fang Zheng, Guo Kai
Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, 30 Puzhu Rd S., Nanjing, 211816, China.
Institute of Nanjing Advanced Biomaterials & Processing Equipment, Nanjing, 210031, P. R. China.
Org Biomol Chem. 2024 Feb 7;22(6):1213-1218. doi: 10.1039/d3ob01864d.
An unprecedented one-pot route to achieve highly regioselective 1-sulfur-functionalized 2-nitrogen-functionalized alkenes and 2-thiocyanate indolines from unsymmetrical ynamides (readily and generally available amides) using the commercially available inexpensive iodobenzene diacetate (PIDA) as the oxidant and potassium thiocyanate (KSCN) as the thiocyanate (SCN) source has been developed. The interconversion of thiocyanate (SCN) and isothiocyanate (NCS) groups simultaneously forms C-N and C-S bonds in this metal-free approach, while introducing important functional groups into homemade alkynes. A radical-chain mechanism, involving competing kinetically controlled chain transfer at the S atom and sterically-controlled chain transfer at the N atom of the thiocyanogen molecule in this mild approach, is proposed.
已经开发出一种前所未有的一锅法路线，使用市售的廉价二醋酸碘苯（PIDA）作为氧化剂，硫氰酸钾（KSCN）作为硫氰酸盐（SCN）源，从不对称烯酰胺（易于普遍获得的酰胺）制备高度区域选择性的1-硫官能化2-氮官能化烯烃和2-硫氰酸酯吲哚啉。在这种无金属方法中，硫氰酸盐（SCN）和异硫氰酸盐（NCS）基团的相互转化同时形成C-N和C-S键，同时将重要的官能团引入自制的炔烃中。提出了一种自由基链机制，该机制涉及在这种温和方法中硫氰分子的S原子上的动力学控制链转移竞争和N原子上的空间控制链转移。
