Pd‐Catalyzed Difluoromethylation of Vinyl Bromides, Triflates, Tosylates, and Nonaflates

Abstract

Pd-catalyzed difluoromethylation of di-, tri- or tetra-substituted vinyl bromides, triflates, tosylates and nonaflates under mild conditions is described. The reaction tolerates a wide range of functional groups, such as bromide, chloride, fluoride, ester, amine, nitrile, and protected carbonyl, thus providing a general route for the preparation of difluoromethylated alkenes.

Difluoromethylation Reactions of Organic Compounds

“…Shen and colleagues have introduced in 2015 a difluoromethylation reaction of vinyl bromides, vinyl triflates, and vinyl tosylates employing [(SIPr)Ag(CF 2 H)] (SIPr=1,3‐bis(2,6‐ diisopropyl phenyl)imidazolin‐2‐ylidene), a nucleophilic difluoromethylating reagent, [{Pd(cinnamyl)Cl} 2 ] as Pd catalyst, DPPF as ligand, in dioxane at 60 °C for 24 h. The scope of the transformations is illustrated in Scheme .…”

Recent Progress toward the Introduction of Functionalized Difluoromethylated Building Blocks onto C(sp2) and C(sp) Centers

“…In 2015, the same research group successfully extended their methodology to the difluoromethylation of vinyl bromides, triflates, tosylates, and nonaflates (Scheme ) 41. In this case, the reaction was carried out by using (SIPr)AgCF 2 H instead of the (SIPr)AgCl/TMSCF 2 H/ t BuONa system, in order to avoid the activation of the allylic CF bond under basic conditions.…”

Recent Progress in the Application of Difluoromethyl Diazomethane as Fluorine-Containing Building Block

“…图 1 含有二氟甲基的药物和生物活性分子 Figure 1 Difluoromethyl-containing drugs and bioactive molecules 近十年来, 二氟甲基化反应得到了快速发展 [4] , 其 中"直接"二氟甲基化和"间接"二氟甲基化反应已被 广泛研究. 研究者开发了许多不同类型的亲电、亲核及 自由基二氟甲基试剂, 如 Ph 3 P ＋ CF 2 2 CO -(PDFA) [5] 、 TMSCF 2 Br [6] 、BrCF 2 H [7] 、TMSCF 2 H [8] 、二氟甲基杂芳 基砜 [9] 、(DMPU) 2 Zn(CF 2 H) 2 [10] 和[(SIPr)Ag-(CF 2 H)] [11] 等. 除此之外, 含二氟甲基砌块参与的化学转化也被用于复 杂含二氟甲基化合物的构建.…”