ABSTRACT Hydroformylation, the conversion of alkenes into aldehydes, is a cornerstone industrial process, as aldehydes serve as versatile intermediates for numerous chemical transformations. Conventionally, this process operates under pressure of CO and H 2 (syngas) and relies on homogeneous catalysis. However, the dependence on toxic, high‐pressure carbon monoxide feedstock presents significant safety and environmental challenges. Herein, we present a perspective on emerging strategies to overcome this critical limitation by developing CO‐free, heterogeneous catalytic systems. We present recent photoredox strategies capable of generating the formyl radical (•CHO), enabling hydroformylation to proceed entirely without CO. Notably, several of these approaches can be adapted to heterogeneous photocatalytic systems, opening the possibility of performing CO‐free hydroformylation under significantly milder conditions while also achieving heterogenization—an enduring goal in this field. This dual advantage positions these emerging methods as promising, greener, and safer alternatives to conventional hydroformylation.
Cunha et al. (Sun,) studied this question.