A strategy is reported in which traceless directing groups (TDGs) are used to promote the redox-neutral Mn -catalyzed regioselective synthesis of N-heterocycles. Alkyne coupling partners bearing a traceless directing group, which serves as both the chelator and internal oxidant, were used to control the regioselectivity of the annulation reactions. This operationally simple approach is highly effective with previously challenging unsymmetrical alkyne systems, including unbiased dialkyl alkynes, with perfect regioselectivity. The simple conditions and the ability to carry out synthesis on a gram scale underscore the usefulness of this method. The application of this strategy in the concise synthesis of the bioactive compound PK11209 and the pharmaceutical moxaverine is also described.

The adoption of new measures that preserve our environment, on which our survival depends, is a necessity. Electro‐organic processes are sustainable per se, by producing the activation of a substrate by electron transfer at normal pressure and room temperature. In the recent years, a highly crescent number of works on organic electrosynthesis are available. Novel strategies at the electrode are being developed enabling the construction of a great variety of complex organic molecules. However, the possibility of being scaled‐up is mandatory in terms of sustainability. Thus, some electrochemical methodologies have demonstrated to report the best results in reducing pollution and saving energy. In this personal account, these methods have been compiled, being organized as follows: • Direct discharge electrosynthesis • Paired electrochemical reactions. and • Organic transformations utilizing electrocatalysis (in absence of heavy metals). Selected protocols are herein presented and discussed with representative recent examples. Final perspectives and reflections are also considered.

A highly selective Mn(I)-catalyzed alkenylation of arenes and heteroarenes with 1,3-diynes is described. The reported transformation overcomes regio-, chemo-, and stereoselectivity challenges associated with the use of these coupling partners. Both symmetrical and unsymmetrical diynes can be applied in this protocol, affording single isomers not only in the synthesis of 1,3-enynes but also in the one-step preparation of pyrroles and furans. This simple strategy features wide functional group tolerance, good reproducibility, and preparative scale utility. The manganese catalyst plays a crucial role in this C−H activation protocol, enabling high selectivity with previously challenging internal alkynes. Furthermore, the synthetic value of the method is highlighted by diverse postsynthesis functionalizations of the final products.

An unprecedented Mn -catalyzed (2-indolyl)methylation of heteroarenes is reported. This method makes use of an aromatizing cascade strategy to install a (2-indolyl)methyl group into target molecules, thereby leading to the expedient synthesis of previously challenging and important unsymmetrical diheteroarylmethanes, in particular bis(2-indolyl)methanes. The proposed cascade process comprises the reorganization of multiple bonds with controlled regioselectivity and high atom economy and can be performed on a gram-scale. Furthermore, a metal-free C-H propargylation is observed. The diverse application of this method is also demonstrated.

A manganese(I)/Lewis acid cocatalyzed direct C-H propargylation with high selectivity has been developed. BPh was discovered to not only promote the reactivity, but also enhance the selectivity. Secondary, tertiary, and even quaternary carbon centers at the propargylic position could be directly constructed. Both internal and terminal alkynes are easily accessible. The chirality was successfully transferred from an axially chiral allene to central chirality. The reactivity of the manganese catalyst in this reaction was found to be unique among transition metal catalysts.