Synthesis of Vinyl Nitriles
A palladium-catalyzed cyanation of alkenyl halides using acetone cyanohydrin enables the preparation of structurally diverse alkenylic nitrile containing compounds in one step. The reaction is efficient, chemoselective, easy to perform, and tolerates a number of functional groups.
K. J. Powell, L-C. Han, P. Sharma, J. E. Moses, Org. Lett., 2014, 16, 2158-2161.
A highly stereo- and regioselective hydrocyanation of terminal alkynes provides E-configured alkenyl nitriles employing acetone cyanohydrin as a practical alternative to HCN gas. Acrylonitriles can be accessed on gram scale with broad substrate scope and functional group tolerance.
F. Ye, J. Chen, T. Ritter, J. Am. Chem. Soc., 2017, 139, 7184-7187.
Lewis-acid catalysts such as AlMe3, AlMe2Cl, and BPh3 significantly improve the efficiency of the nickel-catalyzed aryl- and alkenylcyanation of alkynes. Electron-rich cyanides, which exhibit poor reactivity in the absence of Lewis acids, readily undergo the arylcyanation reaction under the newly disclosed conditions.
Y. Nakao, A. Yada, S. Ebata, T. Hiyama, J. Am. Chem. Soc., 2007, 129, 2428-2429.
A simple three-step single-pot procedure for Z-stereoselective synthesis of β-monosubstituted acrylonitriles involves olefination of aldehydes with an in situ generated α-diaminoboryl carbanion species. Various aromatic and aliphatic aldehydes were smoothly converted into the corresponding (Z)-olefin products in good yields.
T. Tomioka, Y. Takahashi, T. G. Vaughan, T. Yanase, Org. Lett., 2010, 12, 2171-2173.