[3,3]-Sigmatropic Shifts and Retro-ene Rearrangements in Cyanates, Isocyanates, Thiocyanates, and Isothiocyanates of the Form RX-YCN and RX-NCY

Abstract

Retro-ene type [2π + 2π + 2σ] and [3,3]-sigmatropic shift reactions involving the substituent groups R in heteroatom-substituted cyanates and thiocyanates RX-YCN and the isomeric isocyanates and isothiocyanates of the type RX-NCY (X = CR₂, NR′, O, or S; Y = O or S) have been investigated computationally at the B3LYP/6-311++G­(d,p) level. Retro-ene reactions of alkyl derivatives of the title compounds afford alkenes, imines, carbonyl and thiocarbonyl compounds together with HNCO (HNCS) or HOCN (HSCN). [3,3]-Sigmatropic shifts (hetero-Cope rearrangements) of the corresponding allyl, propargyl, benzyl, and aryl derivatives causes allylic rearrangements, propargyl–allenyl rearrangement, conversion of benzyl cyanates to <i>o</i>-isocyanatotoluenes, and conversion of <i>N</i>-cyanatoarylamines to <i>o</i>-isocyanatoanilines, etc. The corresponding rearrangements of allyl thiocyanates, arylamino thiocyanates and isothiocyanates, and arylsulfenyl thiocyanates and isothiocyanates are also described