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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 demand Diels-Alder pyridazine removal reaction between tetrazines and allylic substituted trans -cyclooctenes (TCOs) is a key player in bioorthogonal bond cleavage reactions. Deciding the price of reduction on alkyl