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Pyrroloindolines are widely present in natural products. In this review, we summarize state-of-the-art of catalytic asymmetric synthesis of pyrroloindolines, as well as related applications to natural products total synthesis.

A highly enantioselective [4 + 2] cycloaddition reaction of 1-azadienes with 3-vinylindoles, catalyzed by chiral phosphoric acid has been developed to furnish a range of benzofuran-fused tetrahydropyridines with three contiguous stereogenic centers.

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