Carbene Radicals in Transition-Metal-Catalyzed Reactions

[Image: see text] Discovered as organometallic curiosities in the 1970s, carbene radicals have become a staple in modern-day homogeneous catalysis. Carbene radicals exhibit nucleophilic radical-type reactivity orthogonal to classical electrophilic diamagnetic Fischer carbenes. Their successful catalytic application has led to the synthesis of a myriad of carbo- and heterocycles, ranging from simple cyclopropanes to more challenging eight-membered rings. The field has matured to employ densely functionalized chiral porphyrin-based platforms that exhibit high enantio-, regio-, and stereoselectivity. Thus far the focus has largely been on cobalt-based systems, but interest has been growing for the past few years to expand the application of carbene radicals to other transition metals. This Perspective covers the advances made since 2011 and gives an overview on the coordination chemistry, reactivity, and catalytic application of carbene radical species using transition metal complexes and catalysts.