Photopromoted Synthesis Of Nitrile Compounds Using Iodoacetonitrile As Raw Material

Cyano group is a common functional group,which has the structure of carbon nitrogen triple bond.It has strong polarity and electron absorption.Nitriles containing cyanide groups are increasingly becoming critical synthetic precursors in organic chemistry,because cyanide can be converted to ester,carbonyl,carboxyl,and so on.In addition,many drugs contain cyanide in clinical treatment.The introduction of cyanide can change drug molecules’physicochemical and kinetic properties,as well as,improve the bioavailability of drug molecules.Among the different nitrile derivatives,β,γ-unsaturated nitrile has become an essential precursor in synthetic chemistry and has various biological activities.At present,most of the synthesis methods of nitrile compounds require metal catalysis,high temperature,and toxic cyanide source.It is still urgent to develop a more economical and green method for the synthesis ofβ,γ-unsaturated nitrile.Therefore,we use iodine-acetonitrile as the cyanogen source to achieve cyanomethylation reaction under the induction of visible light without adding oxidant and photosensitizer.In this paper,the decarboxylnitrile methylation of cinnamic acid under light induction and the atom transfer radical addition reaction of olefins/alkynes with ICH₂CN without metal induced by visible light are described.1.We proposed an efficient catalytic method to synthesizeβ,γ-unsaturated nitrile without photosensitizer and metal catalyst.At present,most decarboxylation of unsaturated carboxylic acid requires the addition of additional oxidants or photosensitizers.The reaction synthesizes a series ofβ,γ-unsaturated nitrile compounds at room temperature without the need for oxidants and photosensitizers at room temperature under environmentally friendly conditions,by using blue light irradiation.2.A novel blue-light catalyzed addition of iodine-acetonitrile（ICH₂CN）to olefins/alkynes was studied.Cyano-alkylation products are produced by conjugated olefins/styrene reactions.It is noteworthy that the trans-enyl iodide is the main product,and a reasonable reaction mechanism is proposed.The reaction introduces iodine atoms,opening up the possibility for further transformation.