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Preliminary mechanistic researches demonstrated that the diphosphorylation involves two rounds of PCET-initiated radical relay process. © 2020 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim.The inverse electron need Diels-Alder pyridazine reduction reaction between tetrazines and allylic replaced trans -cyclooctenes (TCOs) is an integral player in bioorthogonal relationship cleavage reactions. Deciding the price of removal on alkylamine substrates has thus far proven hard. Here, w