ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 24, Number 3
JKCSEZ 24(3)
June 20, 1980 

Various radicals may add to isonitriles to give imidoyl radcals RN=CR'. This may be also generated via abstraction of imidoyl hydrogen from imine in the following manner RN=C(H)R' ＋ R"· → RN=CR' ＋ R"-H Imidoyl radicals would be stabilized via two pathways, β-cleavage and atom transfer reactions. β-Cleavage may occur in two directions depending upon structure of the radicals. Cyanide transfer and the "so-called" normal β-cleavage are the two modes of β-cleavage. Addition of t-butoxy radical to t-butyl isocyanide 7 generates an imidoyl radical t-Bu-N=C-O-Bu-t, which undergoes β-cleavage to give t-butyl isocyanate and t-butyl radical. Addition of phenyl radical to 7 forms the intermediate radical t-Bu-N=C-C6H5, which decomposes to give benzonitrile and t-butyl radical. The t-butyl radical generated from the β-cleavage adds to 7 giving the radical t-Bu-N=C-Bu-t, which cleaves only to pivalonitrile and t-butyl radical, inducing radical chain isomerization. Trimethylsilyl radical adds to 7 to give the intermediate t-BuN=C-Si(CH3)3, which collapses to (CH3)3SiCN and a t-butyl radical.