Low-valent early transition metals are often intrinsically highly reactive as a result of their strong propensity toward oxidation to more stable high-valent states. Harnessing these highly reducing complexes for productive reactivity is potentially powerful for C-C bond construction, organic reductions, small-molecule activation and many other reactions that offer orthogonal chemoselectivity and/or regioselectivity patterns to processes promoted by late transition metals. Recent years have seen many exciting new applications of low-valent metals through building new catalytic and/or multicomponent reaction manifolds out of classical reactivity patterns. In this Review, we survey new methods that employ early transition metals and invoke low-valent precursors or intermediates in order to identify common themes and strategies in synthesis and catalysis.

Pyrroles are structurally important heterocycles. However, the synthesis of polysubstituted pyrroles is often challenging. Here, we report a multicomponent, Ti-catalysed formal [2+2+1] reaction of alkynes and diazenes for the oxidative synthesis of penta- and trisubstituted pyrroles: a nitrenoid analogue to classical Pauson-Khand-type syntheses of cyclopentenones. Given the scarcity of early transition-metal redox catalysis, preliminary mechanistic studies are presented. Initial stoichiometric and kinetic studies indicate that the mechanism of this reaction proceeds through a formally Ti(II)/Ti(IV) redox catalytic cycle, in which an azatitanacyclobutene intermediate, resulting from [2+2] alkyne + Ti imido coupling, undergoes a second alkyne insertion followed by reductive elimination to yield pyrrole and a Ti(II) species. The key component for catalytic turnover is the reoxidation of the Ti(II) species to a Ti(IV) imido via the disproportionation of an η(2)-diazene-Ti(II) complex.

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