PLAYING IN THE FRONTIERS OF THE WOODWARD-HOFFMANN RULES

Pericyclic reactions are known for their exquisite selectivity and, in many cases, the formation of multiple chiral centers with a high degree of control. With the advent of accurate computational tools, this control was translated into predictability, and the design and exploitation of this set of reactions opened a new era in organic synthesis. Suddenly, highly complex and profusely decorated polycyclic structures were accessible in relatively short reaction sequences. Out interest in exploring the limits of application of the rules that govern these reactions with ironfist led us to discover a range of eye opening post-transitional effects that are key to ultimately understand reactivity at a microscopic level.