22031-60-3

Upstream product

• 42843-52-7 (E)-3-bromo-3-hexene 
• 143-33-9 sodium cyanide 
• 16645-01-5 (Z)-3-bromo-3-hexene 
• 151-50-8 potassium cyanide 

Relevant academic research and scientific papers

The Cyanation of Vinyl Halides with Alkali Cyanides Catalyzed by Nickel(0)-Phosphine Complexes Generated In Situ: Synthetic and Stereochemical Aspects

The cyanation of β-bromostyrenes catalyzed by Ni(PPh3)n, which was generated in situ from NiBr2(PPh3)2-Zn-PPh3 (Ni:Zn:P=1:3:2 molar ratio), was at first examined with various MCN (M=K, Na)-dipolar aprotic solvent systems by several procedures.The presence of excess cyanide ion inhibited the reaction.However, when the KCN-DMF system with some intermediate cyanide solubility was used, the nitriles were obtained in high yields and high stereoselectivity at 50 deg C by almost all of the procedures attempted.On the contrary, the KCN-HMPA and KCN-MeCN systems with cyanide solubilities accelerated the coupling of the halides to inhibit the cyanation, and in general the NaCN-DMF and NaCN-HMPA systems with high cyanide solubilities needed to reduce Ni(II) before adding MCN in order to make the catalytic reaction start.Vinyl halides such as 1- and 2-halo (Cl, Br)-1-alkenes, 2-bromo-2-butenes, 3-bromo-3-hexenes, and 1-chlorocyclohexene were also cyanated using suitable procedures and MCN-solvent systems to give the corresponding nitriles in high yields and fair-to-good stereoselectivities.However, with (Z)-2-ethoxy-1-bromoethene the (E)-nitrile, though its selectivity markedly varied with the reaction temperature, was obtained as the main product.The cyanation of ethyl (Z)-β-bromoacrylate and ethyl α-bromoacrylate was unsuccessful due to polymerization.

THE CYANATION OF VINYL HALIDES CATALYZED BY NICKEL(0) COMPLEX GENERATED IN SITU

Nickel(0) species generated in situ from NiBr2(PPh3)2-Zn-PPh3 catalyzed the formation of unsaturated nitriles from vinyl halides and potassium cyanide.The reaction proceeded under very mild conditions and was stereoselective.