Understanding cyclobutenone rearrangements: an in silico study

The work described in this thesis sheds new light on the mechanistic pathways followed during thermochemically and photochemically induced cyclobutenone rearrangements through an understanding of thermodynamic and kinetic aspects. The investigation applies DFT and ab initio methods to various rearrangements studied in the laboratory. Energy pathways for various cyclobutenone rearrangements have been developed to rationalise selectivity issues where competitive mechanisms are available. In addition, we have developed models to account for different outcomes observed for organometallic additions to cyclobutenediones. These have, in particular, led to a better understanding of the course of carbonyl addition reactions given by organoytterbium reagents