Addition of Metal Cyanides to Tosylhydrazones of Aldehydes in Aprotic Solvents: A New Method for One-Carbon Homologation of Aldehydes and
for the Synthesis of α-(N ²-Tosylhydrazino)nitriles

Abstract

One-carbon homologation of aldehydes to nitriles via reaction of the respective tosylhydrazones with trimethylsilyl cyanide, tributyltin cyanide and diethylaluminum cyanide with or without Lewis acid-type catalysts was examined. Representative tosylhydrazones on treatment with trimethylsilyl cyanide in the presence of trimethylsilyl triflate or scandium triflate afforded α-(N ²-tosylhydraziono)nitriles in excellent yields. The same adducts were also obtained using tributyltin cyanide/scandium triflate system or diethylaluminum cyanide at room temperature. Treatment of tosylhydrazones with trimethylsilyl cyanide/scandium triflate or with diethylaluminum cyanide in appropriate solvent at higher temperatures afforded the respective one-carbon extended nitriles in good yields. Some examples of the application of these reactions to polyfunctional compounds are given.

Key words

aldehyde arylsulfonylhydrazones - trimethylsilyl cyanide - trimethyltin cyanide - diethylaluminum cyanide - trimethylsilyl triflate - scandium triflate

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