Four-Component Defluorinative Reaction of Allylic Fluorides, Amidines, and Cs₂CO₃ under Transition-Metal-Free Conditions

Y.-L. Chen,^a L.-W. Sun,^a J.-W. Chen,^a M.-Q. Zhu,^a M. Ma,^b Z.-L. Shen,*^a X.-Q. Chu*^a

^a Technical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China.

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

Abstract: Research interest in defluorinative functionzalization by means of the distinctive fluorine effect of organofluorides has led to rapid development in this topic. Herein, we reported an unprecedented four-component defluorinative reaction of allylic fluorides, amidines, and Cs2CO3 for the convenient synthesis of valuable pyrimidine-containing amidino carbamates under transition-metalfree conditions. The synthetic linchpin for realizing the multibonding tandem protocol relied on the directed function of the a- positioned hydroxyl group and the activating effect of the perfluoroalkyl substituent in allylic fluorides. Moreover, cesium carbonate served as a green carbonyl equivalent for formal CO capture. Mechanistic studies revealed that the reaction procceeded via a possible cyclic carbonate intermediate.

Green Chem. 2022, DOI: 10.1039/D2GC02045A. (Impact factor: 11.034)

论文链接：https://pubs.rsc.org/en/Content/ArticleLanding/2022/GC/D2GC02045A