Importantly, the redox handle (e.g. 2,4-dinitrophenol) is critical to the success of these processes, where it serves to lower the reduction potential of the substrate. Motivated by the synthetic utility of Weinreb amides, and conscious of the persistent challenge presented by the parent alkyl derivatives, a redox-neutral, photocatalysis-based platform to enable efficient N-OAlkyl cleavage was devised (Figure ). Addressing this disparity would expand the chemistry of the Weinreb amide moiety beyond acylation and, by unmasking the aldehyde, permit a mild reinterpretation of E. O. Fischer´s celebrated 1908 synthesis of aminoacetaldehyde and related derivatives (Figure , lower left). To that end, a mechanism-guided investigation using the parent Weinreb amide motif was conducted to address reactivity challenges grounded in reduction potential. The reaction design was predicated on a redox neutral N-O cleavage process to simultaneously liberate the (reduced) secondary amide and (oxidized) aldehyde in a single operation (Figure ). This generation of an ambiphilic product lends itself to downstream manipulations in chemical biology with exogenous Lewis bases. It was envisaged that anthracene could be leveraged as a highly reducing photocatalyst (E 0 1/2 = -1.95 V vs SCE) upon excitation at 365 nm. Anthracene has been validated as a competent reducing agent in sensitization-initiated electron transfer for photoredox catalysis, however its use in the title transformation remains unexplored. Through a mechanism-guided approach, the development of a photon induced electron transfer (PET) platform has been validated. Electrochemical limitations have been circumvented by further advancing this platform to leverage consecutive photoinduced electron transfer (ConPET) using 1, 2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) as photocatalyst.