One-carbon-extended nitriles are synthesized by a visible-light-driven 1,2-hydro(cyanomethylation) of alkenes with chloroacetonitrile. A cyanomethyl radical adds onto alkenes to form an alkyl radical, which undergoes hydrogen atom transfer from thiol.
The one-pot iodonium-Claisen rearrangement of aryl iodanes with acetonitrile facilitates the simultaneous incorporation of cyanomethyl and iodide groups into arenes.
Enamine intermediates in the organocatalytic α-cyanomethylation of enolisable aldehydes were identified and their reactivities on the Mayr nucleophilicity scale determined.
The sulfonium–Claisen rearrangement of aryl fluoroalkyl sulfoxides with acetonitrile enables the simultaneous incorporation of a cyanomethyl group and a fluoroalkylthio group into arenes.
Herein, we present a Cu(II)-mediated C–C reaction with α-haloacetonitrile derivatives and aryl tetrahydroisoquinolines via a coupling of C(sp3)–Br and C(sp3)–H bonds, yielding cyanomethylated tetrahydroisoquinolines.