Computational Studies on the Cyclizations of Enediynes, Enyne-Allenes, and Related Polyunsaturated Systems

Abstract

Quantum chemical studies of cyclizations of enediynes and enyne-allenes have proven to be computationally tractable thanks to the success of the unrestricted broken spin symmetry (UBS) approach using GGA functionals for the description of open-shell biradicals; the results can further be improved through single-point energy coupled-cluster computations [CCSD(T), BD(T)]. This made comprehensive computational studies on substituent effects and heterosubstituted systems possible. For convenience and predicting new reactions, these transformations can be grouped within larger "families". Alternative cyclization modes are predicted and await experimental realization.