The mechanisms of the cycloadditions of singlet heterocarbenes and heterocyclic carbenes to alkenes to form heterocyclopropanes and spirocyclopropanes, respectively, have been investigated using CBS-QB3, Density Functional Theory (B3LYP, B3PW91, PBE1PBE) with the 6-311+G(d,p) basis set, and coupled-cluster theory  [CCSD(T) and quadratic configuration interaction method [QCISD(T)] with the cc-pVDZ and cc-pVTZ basis sets. Among the carbenes studied are substituted aminocarbenes, 1,2-dihydro-3H-pyrazol-3-ylidene, 1,2,4,5-tetrahydro-3H-pyrazol-3-ylidene, 1,3-dioxa-2-ylidene, 1,3-dithia-2-ylidene, 1,3-diselenol-2-ylidene, 1,3-oxazol-2-ylidene, 1,2,4-azadiphosphol-3-ylidene, and 1,3-dihydro-1,3-diphosphol-4-azol-2-ylidene.

Philicity of heterocarbenes and heterocyclic carbenes: Mechanisms of 1,2-cycloadditions to alkenes

243rd National Meeting (2012)

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