The manganese-catalyzed addition of C-2 position of indoles to maleimides has been achieved under additive-free conditions. The manganese catalyst exhibits excellent chemo- and regioselectivity, good functional group compatibility, and high catalytic efficiency. The substrate scope can also be extended to maleates, ethyl acrylate, 1,4-dihydro-1,4-epoxynaphthalene, pyrroles, and 2-phenylpyridine, which further demonstrates the universality of this straightforward approach.

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The first Ni(ii)-catalyzed direct sulfuration/annulation of C(sp2)–H bonds with elemental sulfur was developed to afford structurally diverse benzoisothiazolones with benzimidazole skeletons in high yields.

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