Four-Component Defluorinative Reaction of Allylic Fluorides, Amidines, and Cs₂CO₃under Transition-Metal-Free Conditions

Y.-L. Chen,^aL.-W. Sun,^aJ.-W. Chen,^aM.-Q. Zhu,^aM. Ma,^bZ.-L. Shen,*^aX.-Q. Chu*^a

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

^bDepartment 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 thea- 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