A New High-Yield One-Step Synthesis of Phenylpropynenitrile

Copper‐Catalyzed Stereoselective Hydroarylation of 3‐Aryl‐2‐ propynenitriles with Arylboronic Acids

“…The literature precedents require the toxic cyanide nucleophile CuCN [8] or cyano electrophiles such as BrCN [9] or PhOCN. [10] Therefore, we used diethyl cyanomethylphosphonate as a less toxic nitrile precursor.…”

“…Our investigations commenced with the development of a new method for the preparation of cyanoal-kyne substrates 1a-c from readily available arylaldehydes (Scheme 1). The literature precedents require the toxic cyanide nucleophile CuCN [8] or cyano electrophiles such as BrCN [9] or PhOCN. [10] Therefore, we used diethyl cyanomethylphosphonate as a less toxic nitrile precursor.…”

Syntheses and Applications of 2‐Alkynylnitriles

“…The first, high yield, one step synthesis of the simplest arylpropynenitrile i.e 3-phenyl-2-propynylnitrile (3) was achieved by Campagnon et al in 1976 by the treatment of copper (I) phenylacetylenide (1) with cyanogen bromide (2) in dry acetonitrile/diethyl ether at 35°C and eliminated the possibility of formation of 1-bromo-2-phenylacetylene (Scheme 1). [9] In 1980, Zweifel and co-worker employed an electrophilic cyanating reagent i.e phenyl cyanate for the synthesis of various 2-alkynylnitriles by its treatment with lithium acetylides at À 70°C. [10] The strategy has been successfully exploited for the synthesis of 2-alkynylnitriles in high yields (Scheme 2).…”

“…In 1969, Bruce and co-worker found that the reaction of dicyanoacetylenes with transition metal complexes like Fe 2 (CO) 9 , Mn(CO) 5 Br or ferrocene resulted in the formation of black tar due to extreme reactivity of alkyne. They were successful in characterizing the product of reaction between dicyanoacetylene and Vaska's complex and nickelocene to obtain η 2 -bonded three membered ring.…”

Transition Metal‐Free Approach to Propynenitriles and 3‐Chloropropenenitriles

“…[3] There have been slight variations to this three-step process by way of changing the dehydration reagent from trichlorophosphate to acetic anhydride, [4] attemptingi t as ao ne-pot process [5] or achieving the synthesis by ac ontinuousf low method. [6] Af undamental strategy employed widely for the preparation of alkynenitriles 1 involves introduction of ac yano group to the terminal alkyne via metal acetylide and using cyanating agents such as cyanogen bromide, [7] cyanogen iodide, [8] cuprous cyanide, [9] 1-cyanobenzotriazole, [10] phenyl cyanate, [11] 1-cyanoimidazole, [12] and 2-pyridyl cyanate [13] [Eq. (2), Scheme 1].T he transformation of af unctional group such as aldehyde,a lcohol, amide, azide,e tc.…”