Na₂S·9H₂O Enabled Defluorodisulfuration and Hydrodefluorination

of Perfluorobutyl Tetralones: Synthesis of Trifluoromethyl 1,2-

Dithioles

Zi-Lun Yu,^a Man-Hang Feng,^a Peng-Yuan Zhang,^a Hao Xu,^a Danhua Ge,^a Mengtao Ma,^b Zhi-Liang Shen,^*,a

and Xue-Qiang Chu^*,a

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

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

Abstract: An unprecedented defluorocyclization of perfluorobutyl tetralones with Na₂S‧9H₂O was developed for the synthesis of tri-fluoromethyl 1,2-dithioles, which provided chemists novel access to biologically and pharmaceutically relevant organofluo-rides. Successive C(sp³)-F bond functionalization at the perfluoroalkyl chain is vital for four C-H/C-S/S-S bonds formation and a five-membered S-heterocycle assembly. Cheap, low-toxic, and odorless inorganic sulfide Na₂S‧9H₂O acts as both a disulfurating precursor and a hydrodefluorinating reagent in this tandem multi-bond-interconverting reaction.

Organic Letters 2023, 25, 4388-4393. (Impact factor: 5.2)

论文链接：https://pubs.acs.org/doi/10.1021/acs.orglett.3c01573