Iodine(III) promotes cross-dehydrogenative coupling of N-hydroxyphthalimide and unactivated C(sp3)-H bonds

Fufang Wu; Xuanzhen Han; Xuejian Li; Xiaobao Shen; Chang Wang; Zhimei Tian; Bin Cheng; Jingbin Zhang; Liangquan Sheng; Hongbin Zhai

doi:10.1038/s42004-021-00480-8

Iodine(III) promotes cross-dehydrogenative coupling of N-hydroxyphthalimide and unactivated C(sp³)-H bonds

Commun Chem. 2021 Mar 31;4(1):46. doi: 10.1038/s42004-021-00480-8.

Authors

Fufang Wu¹, Xuanzhen Han^{2

3}, Xuejian Li², Xiaobao Shen², Chang Wang², Zhimei Tian², Bin Cheng⁴, Jingbin Zhang⁵, Liangquan Sheng⁶, Hongbin Zhai⁷

Affiliations

¹ Engineering Research Centre of Biomass Conversion and Pollution Prevention Control of Anhui Provincial Department of Education, Fuyang Normal University, Fuyang, China. fufang_wu@foxmail.com.
² Engineering Research Centre of Biomass Conversion and Pollution Prevention Control of Anhui Provincial Department of Education, Fuyang Normal University, Fuyang, China.
³ State Key Laboratory of Chemical Oncogenomics, Shenzhen Engineering Laboratory of Nano Drug Slow-Release, Peking University Shenzhen Graduate School, Shenzhen, China.
⁴ Institute of Marine Biomedicine, Shenzhen Polytechnic, Shenzhen, China.
⁵ Youcare Pharmaceutical Group CO, LTD, Fuyang, China.
⁶ Engineering Research Centre of Biomass Conversion and Pollution Prevention Control of Anhui Provincial Department of Education, Fuyang Normal University, Fuyang, China. shenglq@fync.edu.cn.
⁷ State Key Laboratory of Chemical Oncogenomics, Shenzhen Engineering Laboratory of Nano Drug Slow-Release, Peking University Shenzhen Graduate School, Shenzhen, China. zhaihb@pku.edu.cn.

Abstract

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(sp³)-H bond activation under mild reaction conditions. O-substituted NHPI derivatives are generated in good yields under metal-free conditions.