Formaldehyde-Extruding Homolytic Aromatic Substitution via C→O Transposition: Selective 'Traceless-Linker' access to Congested Biaryl Bonds

Abstract

A new, selective way to form C-C bonds has been developed. In this report, we disclose the homolytic aromatic substitution via C→O transposition coupled with the elimination of formaldehyde (as a traceless linker). Computational analysis indicates the selectivity can be tuned by sterics in the starting materials following an ipso-attack that leads to the C→O transposition.

Keywords: C−C coupling; density functional calculations; radicals; reaction mechanisms; spiro compounds.