Chapter 2.4 - Molecular rearrangements

Abstract

In view of the high electrophilicity of arynes, a wide range of nucleophiles can add to the strained carbon-carbon triple bond of arynes generating the zwitterionic intermediates. In some cases, the zwitterions thus generated can undergo molecular rearrangements under mild conditions leading to the synthesis of useful products. These aryne-triggered rearrangements allow functional group transposition, skeletal construction, ring formation, ring contraction, ring expansion, and even chirality transfer. Several complex synthetically valuable molecules can be synthesized employing the aryne-triggered rearrangements strategy, which are otherwise difficult to construct using common methods. Herein, we summarize the advances in aryne-triggered molecular rearrangements.