Yasuhiro Yamasaki

Reaction of F-alkanoic acid chlorides with trialkyl phosphites leading to 1-(dialkoxyphosphinyl)oxy-f-1-alkenephosphonates or 1-(dialkoxyphosphinyl)oxy-1H-F-alkanephosphonates☆

Abstract F -Alkanoic acid chlorides exothermically reacted with 2 equivalents of trialkyl phosphite without solvent at −20 °C to ambient temperature to give the corresponding dialkyl ( Z )-1- (dialkoxyphosphinyl)oxy- F -1-alkenephosphonate in high yields. When the reaction was conducted at −78 °C in an ethereal solvent, dialkyl 1-(dialkoxyphosphinyl)oxy-1 H - F -alkanephosphonate was obtained exclusively in place of the former alkenephosphonate. No F -acylphosphonate was detected in spite of the amount of the phosphite, the mode of addition, and the reaction temperature being varied.

New fluoride ion-catalyzed reaction of f-alkylacetylenes with silyl enol ethers. An efficient route to f-alkyl-substituted propargylic alcohols and α-hydroxy ketones

Abstract Treatment of F -alkylacetylenes, generated in situ from 1 H - F -1- alkenephosphonates, with silyl enol ethers in the presence of a catalytic amount of tetrabutylammonium fluoride gives good yields of F -alkyl-substituted propargyl alcohols or 4-(1 H - F -alkylidene)-1,3-dioxolane derivatives, the latter being converted to tie corresponding α-hydroxy ketones.

A novel reaction of 1-phosphonyloxy-F-1-alkenephosphonates: highly effective method for the synthesis of α,β-unsaturated F-carboxylic acid derivatives

Abstract 1-Phosphonyloxy- F -1-alkenephosphonates, easily prepared from F -alkanoic acid chlorides and triethyl phosphite, undergo a unique fluoride ion-catalyzed reaction with primary and secondary amines or alcohols to afford the corresponding α, β-unsaturated F -carboxylic acid derivatives in excellent yields, along with diethyl fluorophosphate and phosphite.

A New, Effective Method for the Synthesis of 1H-F-1-Alkene-1-phosphonates from F-Alkanoic Acid Chlorides

Abstract Diethyl ( Z )-1 H - F -1-alkene-1-phosphonates were synthesized in good yields by the treatment of diethyl ( Z )-1-[(diethoxyphosphinyl) oxy]- F -1-alkene-1-phosphonates, prepared from F - alkanoic acid chlorides and triethyl phosphite, with butylcopper (I) reagent in tetrahydrofuran-tetramethylethylenediamine at −78 °C.