Preparation of Aromatic and Heterocyclic Amines by the Electrophilic Amination of Functionalized Diorganozincs with Polyfunctional -2,6-Dichlorobenzoyl Hydroxylamines.

We report a catalyst-free electrophilic amination, which enables the synthesis of aromatic and heterocyclic amines. By subjecting diarylzinc or diheteroarylzinc compounds to readily accessible -2,6-dichlorobenzoyl hydroxylamines in the presence of MgCl in dioxane at a temperature of 60 °C (8-16 h). This new electrophilic amination allowed an expedited synthesis of two pharmaceutically significant compounds: vortioxetine is a key intermediate of delamanid.

Lanthanum-Catalyzed Stereospecific Cross-Coupling of Propargylic Substrates with Grignard Reagents.

Transition-metal-catalyzed cross-coupling of propargylic electrophiles and Grignard reagents provides densely functionalized products that are extremely useful synthetic intermediates. However, examples of conversion of propargylic derivatives to form propargyl compounds remain limited due to the challenging regioselectivity. We use LaCl·2LiCl to catalyze propargylation of Grignard reagents in the absence of ligand in high regioselectivity and stereospecificity.

Electrochemical Reductive Arylation of Nitroarenes with Arylboronic Acids.

The synthesis of diarylamine is extremely important in organic chemistry. Herein, a novel electrochemical reductive arylation of nitroarenes with arylboronic acids was developed. A variety of diarylamines were synthesized without the need for transition-metal catalysts.