A High Level Ab initio Study of Thermal 1,3-Sigmatropic Shift in CH2=CHCH2X

초록

The thermal 1,3-sigmatropic migrations in X-CH2-CH=CH2 with X=BH2, NH2 and CH3 have been investigated at the RHF, MP2, B3LYP, G3 and CBS-APNO levels. In all three cases, the suprafacial allowed path proceeds through a TS in which the C=C p electron is delocalized into the 2p AO in the migrating X.