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Manganese-catalyzed sequential C–H and C–C/C–Het bond activation to synthesize allylic alcohols, allylated arenes, functionalized cyclopentenes and skipped dienes is reported. This protocol can be readily scaled up and various coupling partners are applied in manganese catalysis for the first time. Moreover, manganese-catalyzed alkenyl C(sp2)–H activation is also shown. Complimentary to the standard solution-based protocols, these reactions also proceed efficiently under neat conditions, which is unprecedented for abundant metal catalyzed C–H activation reactions.

Graphical abstract: Manganese-catalyzed allylation via sequential C–H and C–C/C–Het bond activation

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