General-acid catalysis of the reaction of methoxyamine with phenyl acetate by the proton, carboxylic acids, and ammonium ions follows a nonlinear Bransted curve. This curve agrees quantitatively with the behavior expected for the enforced preassociation mechanism of catalysis that was predicted for this reaction. The stronger acids, including the proton, follow a Bransted slope of a = 0.16 that...

The combination of photoredox catalysis and enamine catalysis has enabled the development of an enantioselective a-cyanoalkylation of aldehydes. This synergistic catalysis protocol allows for the coupling of two highly versatile yet orthogonal functionalities, allowing rapid diversification of the oxonitrile products to a wide array of medicinally relevant derivatives and heterocycles. This met...

•Relay process for the controllable formation of N-centered radicals under visible light•Amidation aldehydes catalyst-, oxidant-, and coupling-reagent-free conditions•Atom economic transformation that results in NaCl as only byproduct•Broad scope high functional group tolerance leading to excellent applicability Amides are an important class structural motifs prevalently found bioactive compoun...