Direct and Versatile Synthesis of Red-Shifted Azobenzenes

Abstract

A straightforward synthesis of azobenzenes with bathochromically-shifted absorption bands is presented. It employs an ortho-lithiation of aromatic substrates, followed by a coupling reaction with aryldiazonium salts. The products are obtained with good to excellent yields after simple purification. Moreover, with the presented methodology, a structurally diverse panel of different azobenzenes, including unsymmetric tetra-ortho-substituted ones, can be readily obtained, which paves the way for future development of red-light-addressable azobenzene derivatives for in vivo application.

Keywords: azobenzenes; diazonium salts; lithiation; photochromism; red shift.