α-Fluoroacrylonitriles: Horner–Wittig synthesis and conversion into 2-fluoroallylamines and C-(1-fluorovinyl)nitrones

Synthesis and Diels–Alder reactions of α-fluoro- and α-trifluoromethylacrylonitriles

“…E-and Zisomers mixture of alkenes could not be separated by column chromatography. 1 H NMR and 13 C NMR spectra of compounds (3b, 3c, 3i) are in agreement with published data [36].…”

“…Different synthetic approaches have been proposed for synthesis of 2-fluoroacrylonitriles [28,31,[32][33][34][35][36]. The most general route is based on the Horner-Wadsworth-Emmons (HWE) reaction of a cyanofluoromethyl-substituted phosphonate with carbonyl compounds [31,32,36,37].…”

“…The most general route is based on the Horner-Wadsworth-Emmons (HWE) reaction of a cyanofluoromethyl-substituted phosphonate with carbonyl compounds [31,32,36,37]. But usually, these reactions proceed with low stereoselectivity and require utilization of absolute solvents, organometallic and toxic organophosphorous compounds.…”

Synthesis of Fluoroolefins via Julia-Kocienski Olefination

“…Known methods for the synthesis of a-fluoroacrylonitriles involve use of diethyl (cyano)(fluoro)methanephosphonate 36 or (diphenylphosphinoyl)fluoroacetonitrile, 37 both derived from fluoroacetonitrile. In each case it was necessary to prepare the reagent in situ in order to obtain good condensation yields.…”

Fluoro-Julia Olefination as a Mild, High-Yielding Route to α-Fluoro Acrylonitriles

“…Although the HWE reagent prepared in this manner was isolated, its use in condensation reactions with aldehydes and ketones was successful only when prepared in situ. Van der Gen et al11 prepared (diphenylphosphinoyl)fluoroacetonitrile in situ from the fluoroacetonitrile anion, but attempts at its isolation were unsuccessful 11. Condensations proceeded with aldehydes as well as ketones in reasonable yields.…”