Arynes in sigma-Insertion Reactions and as Radical Acceptors

Basic data for this project

Description

In situ generated arynes have recently gained great attention in synthetic organic chemistry. This is due to the development of reliable procedures for their clean generation. Many interesting and valuable methods utilizing arynes as intermediates have been disclosed. Arynes are well known to react in cycloaddition type reactions for the construction of benzannellated (hetero)cycles. Moreover, these reactive intermediates are known to directly insert into various sigma-bonds and various reactions with nucleophiles have been reported where the arynes act as electrophiles. Arynes can be considered as alpha-diaryl radicals. However, radical chemistry of arynes as radical acceptors has not been well investigated to date. The research project focusses on the study of the reactivity of in situ generated arynes towards various radicals. The challenge is the concomitant generation of radicals and arynes. Special focus will be paid towards radical atom and group transfer reactions using arynes as acceptors. The second part of the proposal is dealing with novel sigma-bond insertion reactions by using neutral nucleophiles. Aryne insertion reactions that comprise sigmatropic rearrangements will also be investigated.