Acceptorless dehydrogenative coupling reactions has emerged as one of the promising technique in synthetic organic chemistry to construct carbon‐carbon and carbon‐heteroatom bonds in an environmentally benign and sustainable way. The methodology is highly atom economical and produces water and hydrogen as the byproducts. This protocol, coupled with the earth‐abundant and less toxic manganese catalyst provides a unique opportunity to construct various synthons and biologically important motifs. In recent years, tremendous progress has been made with manganese catalysis based on the pincer ligands for various homogeneous transformations. This review covers the recent progress in the field of manganese catalyzed acceptorless dehydrogenative coupling reactions, their scope and brief mechanistic discussion.

N-alkylation of amines is an important catalytic reaction in synthetic chemistry. Herein, we report a simple strategy for the N-alkylation of 2-aminopyridines with 1,2-diketones using BF3·OEt2 as a catalyst. The reaction proceeds under aerobic conditions, leading to the formation of a diverse range of substituted secondary amines in good to excellent yields. A close inspection of the mechanistic pathway using various spectroscopic techniques and the computational study revealed that the reaction proceeds through the formation of an iminium–keto intermediate with the liberation of CO2.

A sustainable and cost‐effective protocol has been reported for the synthesis of amide bonds from unactivated esters and non‐nucleophilic amines promoted by potassium tert‐butoxide under aerobic conditions. The reaction proceeds under relatively mild conditions, encompassing wide substrate scope. A combined experimental and quantum chemical study has been performed to shed light on the mechanism, which implied that a radical pathway is operating for the present protocol.