Photocatalyzed Oxidative Tandem Reaction Mediated by Bipyridinium for Multifunctional Derivatization of Alcohols

The multifunctional derivatization of alcohols has been achieved by the bipyridinium‐based conjugated small molecule photocatalysts with redox center and Lewis acid site. Besides exhibiting high activity in the selective generation of aldehydes/ketones, acids from alcohols through solvent modulation, this system renders the first selective synthesis of esters via an attractive cross‐coupling pattern, whose reaction route is significantly different from the traditional condensation of alcohols and acids or esterification from hemiacetals. Following the oxidization of alcohol to aldehyde via bipyridinium‐mediated electron and energy transfer, the Lewis acid site of bipyridinium further then activates the aldehyde and methanol to obtain the acetal, which further reacts with methanol to generate ester. This method not only demonstrates a clear advantage of bipyridinium in diverse catalytic activities, but also paves the way for designing efficient multifunctional small molecule photocatalysts. This metal‐ and additive‐free photocatalytic esterification reaction marks a significant advancement towards a more environmentally friendly, cost‐effective and green sustainable approach, attributed to the utilization of renewable substrate alcohol and the abundant, lowcost air as the oxidant. The mildness of this esterification reaction conditions provides a more suitable alternative for large‐scale industrial production of esters.