Li Jing, Jiao Jiajun, Zhang Caiyun, Shi Min, Zhang Jun
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry&Molecular Engineering, East China University of Science and Technology, 130 Mei Long Road, Shanghai, 200237, China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai, 200032, China.
Chem Asian J. 2016 May 6;11(9):1361-5. doi: 10.1002/asia.201600182. Epub 2016 Mar 30.
We have developed I2 - or N-iodosuccinimide (NIS)-mediated amidiniumation of N-alkenyl formamidines for the syntheses of cyclic formamidinium salts, some of which could be directly used as N-heterocyclic carbene (NHC) precursors. Treatment of iodine-containing formamidinium salts with Al2 O3 led to the formation of cyclic formamidinium salts with an unsaturated backbone. A rhodium(I) complex ligated by a representative NHC was prepared by the reaction of [Rh(cod)Cl]2 (cod=1,5-cyclooctadiene) with the free carbene obtained in situ from deprotonation of the corresponding formamidinium salts. The NHCs prepared in situ can also react with S8 to afford the corresponding thiones.
我们已经开发出碘（I₂）或N - 碘代琥珀酰亚胺（NIS）介导的N - 烯基甲脒的脒基化反应，用于合成环状甲脒盐，其中一些可直接用作N - 杂环卡宾（NHC）前体。用Al₂O₃处理含碘甲脒盐会导致形成具有不饱和主链的环状甲脒盐。通过[Rh(cod)Cl]₂（cod = 1,5 - 环辛二烯）与由相应甲脒盐去质子化原位获得的游离卡宾反应，制备了一种由代表性NHC配位的铑（I）配合物。原位制备的NHC也能与S₈反应生成相应的硫酮。
