Water-Promoted Defluorinative Synthesis of Fluoroalkylated 1,5- Diazapentadienes by Using (NH₄)₂CO₃ as NH₂ and NH Sources

Wei Han,^a,# Yu-Lan Chen,^a,# Xi Tang,^a Jie Zhou,^*b Mengtao Ma,^c Zhi-Liang Shen,^*a and Xue-Qiang Chu^*a

^a Technical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China. E-mail: xueqiangchu@njtech.edu.cn; ias_zlshen@njtech.edu.cn.

^b State Key Laboratory of Materials-Oriented Chemical Engineering, College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211816, China. E-mail: jayzhou@njtech.edu.cn.

^c Department of Chemistry and Materials Science, College of Science, Nanjing Forestry University, Nanjing 210037, China.

^# These authors contributed equally to this work.

Abstract: A H₂O-promoted and (NH₄)₂CO₃-enabled deiodoamination and defluoroiminizative reaction of fluoroalkyl alkenes has been developed under transition-metal-free conditions. Structurally important fluoroalkylated 1,5-diazapentadienes were obtained in excellent Z-selectivity with good functional group tolerance. The versatility of the method was illustrated in the synthesis of valuable organofluorides commencing from the obtained products. Compared to traditional synthetic methods, several apparent limitations, including distillation for purification, multistep manipulation, harsh reaction conditions, moisture exclusion, and the use of toxic/sensitive reagents, could be avoided. The key to the success of the reaction is the use of (NH₄)₂CO₃ as commercially available, inexpensive, low-toxic, and efficient NH₂/NH sources and water as a C(sp³)-F bond cleavage promoter. Moreover, the distinctive fluorine effects of perfluoroalkyl substituents on substrates are also vital for enhancing the reaction efficiency.

Green Chemistry 2023, 25, 9672-9679. (Impact factor: 9.8)

论文链接：https://pubs.rsc.org/en/content/articlelanding/2023/gc/d3gc03717g/unauth