Wu Fufang, Han Xuanzhen, Li Xuejian, Shen Xiaobao, Wang Chang, Tian Zhimei, Cheng Bin, Zhang Jingbin, Sheng Liangquan, Zhai Hongbin
Engineering Research Centre of Biomass Conversion and Pollution Prevention Control of Anhui Provincial Department of Education, Fuyang Normal University, Fuyang, China.
State Key Laboratory of Chemical Oncogenomics, Shenzhen Engineering Laboratory of Nano Drug Slow-Release, Peking University Shenzhen Graduate School, Shenzhen, China.
Commun Chem. 2021 Mar 31;4(1):46. doi: 10.1038/s42004-021-00480-8.
Cross-dehydrogenative coupling reactions provide a method to construct new chemical bonds by direct C-H activation without any pre-functionalization. Compared to functionalization of a C-H bond α- to ether oxygen, α- to carbonyl, or at a benzylic position, functionalization of unactivated hydrocarbons is difficult and often requires high temperatures, a transition-metal catalyst, or a superstoichiometric quantity of volatile, toxic, and explosive tert-butylhydroperoxide. Here, a cross-dehydrogenative C-O coupling reaction of N-hydroxyphthalimide with unactivated alkanes, nitriles, ethers, and thioethers has been realized by using iodobenzene diacetate as the radical initiator. The current protocol enables efficient functionalization of unactivated hydrocarbons and nitriles through inert C(sp)-H bond activation under mild reaction conditions. O-substituted NHPI derivatives are generated in good yields under metal-free conditions.
交叉脱氢偶联反应提供了一种通过直接C-H活化来构建新化学键的方法，无需任何预官能团化。与C-H键在醚氧的α位、羰基的α位或苄基位置的官能团化相比，未活化烃的官能团化较为困难，通常需要高温、过渡金属催化剂或化学计量过量的挥发性、有毒且易爆的叔丁基过氧化氢。在此，通过使用二醋酸碘苯作为自由基引发剂，实现了N-羟基邻苯二甲酰亚胺与未活化烷烃、腈、醚和硫醚的交叉脱氢C-O偶联反应。当前的方法能够在温和的反应条件下通过惰性C(sp)-H键活化实现未活化烃和腈的高效官能团化。在无金属条件下能以良好的产率生成O-取代的NHPI衍生物。
