A significantly improved method for metal-free biaryl synthesis through the photochemical extrusion of traceless linkers (photosplicing) is presented. An array of aldehydes and ketones have been identified as powerful photosensitizers that eliminate the requirement for UV−C light, allowing the use of UV LEDs and even sunlight. This advancement not only simplifies the reaction setup but also enables the scalable production of biphenyls.

Abstract

The regioselective synthesis of biphenyls, which are economically important pharmaceuticals, agrochemicals, and liquid crystals, is a challenging task. Current methods rely on metal-dependent cross-coupling reactions, which unfortunately require the use of harmful halogenated aryls and heavy metal catalysts that are toxic and difficult to remove from the final products. Recently, we have circumvented these problems by developing a metal-free and broadly applicable photochemical method for biphenyl synthesis using UV−C light, called photosplicing. Here we present an improved method using photosensitizers in combination with UV−B, UV−A light, or sunlight. Using a high-precision flow reactor with deep-UV LEDs, we investigated the ability of commonly available organic photosensitizers to enhance the photosplicing reaction and identified a number of suitable photosensitizers with the required triplet energy. This method allows for easy batch synthesis of biaryls in borosilicate glassware and paves the way for their large-scale production without the need for flow reactors.