Oxidative Heck Reaction of Fluorinated Olefins with Arylboronic Acids by Palladium Catalysis

Abstract

The palladium‐catalyzed oxidative Heck reaction of 2,3,3,3‐tetrafluoroprop‐1‐ene with various arylboronic acids was explored for the first time. This method provides a direct route to access (Z)‐β‐fluoro‐β‐(trifluoromethyl)styrenes with high stereoselectivity.

Consecutive Transformations of Tetrafluoropropenes: Hydrogermylation and Catalytic C−F Activation Steps at a Lewis Acidic Aluminum Fluoride

“…Thec atalytic hydrodefluorinationofC(sp 3 )ÀFbonds at fluorinated alkanes was reported in the homogeneous phase,f or instance with silylium ions as the catalyst. [14] HFO-1234ze (2), whichi sa ni somero fH FO-1234yf (1), waso nlya pplied in hydrosilylationr eactions with HSiCl 3 , [15] andp atents coverthe addition of HF,C l 2 ,o rH 2 . [10] However,the decompositionofHFO-1234yf(1)inthe atmosphere or at high temperatures is also amatterofdiscussion.…”

“…Finally,t he generation of 10 a-10 c occurs via additional hydrogermylation steps at 3,3,3-trifluoropropene (14), which were also investigated by irradiation at 311 nm. Again, ACF did not affect the hydrogermylation, but heating asolution of 14 for 4h at 70 8 8Ci nt he absence of ACFg ave 24 % conversion.…”

“…[11] Scarce reactivity studieso f1 includer eactions towardsa lkoxides, [12] alcohols, [13] ando xidative Heck reactionsw itha rylb oronic acids. [14] HFO-1234ze (2), whichi sa ni somero fH FO-1234yf (1), waso nlya pplied in hydrosilylationr eactions with HSiCl 3 , [15] andp atents coverthe addition of HF,C l 2 ,o rH 2 . [16] Herein, we report the distinct reactivity of tertiary germanes and Et 3 SiH towards HFO-1234yf (1)a nd HFO-1234ze (2)i nt he presence of ACFa sac atalyst under very moderate reaction conditions.W ith Et 3 SiH, rare monodefluorinations at trifluoromethyl groups were achieved.…”

Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents as the Cross-Coupling Partners

“…The reaction presumably proceeded via (1) oxidative addition of aryldiazonium salt (106) to Pd(0), leading to an arylpalladium complex (110), (2) Arylboronic acids are an important class of compounds for coupling reactions, which are stable in air and to moisture, and they are compatible with a broad range of common functional groups [62][63][64]. In 2015, Lu and co-workers presented the first oxidative Heck-type reactions of arylboronic acids with fluoroalkylated olefin [79]. The Pd-catalyzed cross-couplings of the commercially available 2,3,3,3-tetrafluoroprop-1-ene (116) with diverse arylboronic acids (115) provided a variety of (Z)-β-fluoro-β-(trifluoromethyl)styrene derivatives (117) in good yields (Scheme 22) [79].…”

“…In 2015, Lu and co-workers presented the first oxidative Heck-type reactions of arylboronic acids with fluoroalkylated olefin [79]. The Pd-catalyzed cross-couplings of the commercially available 2,3,3,3-tetrafluoroprop-1-ene (116) with diverse arylboronic acids (115) provided a variety of (Z)-β-fluoro-β-(trifluoromethyl)styrene derivatives (117) in good yields (Scheme 22) [79]. The wide range of substrates and the good functional group tolerance made this strategy facile and practical for the streamlined synthesis of functional styrenes.…”