Oxalamide ligands with additional coordinating groups for Cu-catalyzed arylation of alcohols and phenols.

A novel class of chain-like multidentate oxalamide ligands with additional coordinating groups was developed for the coupling of (hetero)aryl bromides with both alcohols and phenols under mild conditions. Introduction of oxygen atoms in N-alkyl chains is pivotal for the high catalytic efficiency and broad substrate versatility.

Iridium-Catalyzed Asymmetric Hydrogenation of Simple Ketones with Tridentate PNN Ligands Bearing Unsymmetrical Vicinal Diamines.

An iridium catalytic system with a ferrocene-based phosphine ligand bearing a modular and tunable unsymmetrical vicinal diamine scaffold was developed for the asymmetric hydrogenation of aryl ketones. This approach provided a powerful tool for the enantioselective synthesis of diverse chiral alcohols with excellent reactivity and enantioselectivity (up to 99% yield, up to 99% ee, and up to 50,000 turnover number). The substituents and chirality of unsymmetrical diamines in ligands played an important role in the satisfactory results.

Rapid Synthesis of α-Chiral Piperidines via a Highly Diastereoselective Continuous Flow Protocol.

A practical continuous flow protocol has been developed using readily accessible N-(tert-butylsulfinyl)-bromoimine and Grignard reagents, providing various functionalized piperidines (34 examples) in superior results (typically >80% yield and with >90:10 dr) within minutes. The high-performance scale-up is smoothly carried out, and efficient synthesis of the drug precursor further showcases its utility. This flow process offers rapid and scalable access to enantioenriched α-substituted piperidines.

Aminomethylation of Aryl Bromides by Nickel-Catalyzed Electrochemical Redox Neutral Cross Coupling.

We develop an electrochemical nickel-catalyzed aminomethylation of aryl bromides under mild conditions. The convergent paired electrolysis makes full use of anode and cathode processes, free of a terminal oxidant, a sacrificial anode, a metal reductant, and a prefunctionalized radical precursor. In addition, this method exhibits wide functional group tolerance (63 examples), including some sensitive substituents and aromatic heterocycles. This redox neutral cross coupling provides a more environmentally friendly and synthetic practical protocol for forging C(sp2)-C(sp3) bonds.

Direct Arylation of α-Amino C(sp3 )-H Bonds by Convergent Paired Electrolysis.

A metal-free convergent paired electrolysis strategy to synthesize benzylic amines through direct arylation of tertiary amines and benzonitrile derivatives at room temperature has been developed. This TEMPO-mediated electrocatalytic reaction makes full use of both anodic oxidation and cathodic reduction without metals or stoichiometric oxidants, thus showing great potential and advantages for practical synthesis. This convergent paired electrolysis method provides a straightforward and powerful means to activate C-H bonds and realize cross-coupling with cathodically generated species.

Electrochemical [4+2] Annulation-Rearrangement-Aromatization of Styrenes: Synthesis of Naphthalene Derivatives.

We report the first electrochemical strategy to synthesize functionalized naphthalene derivatives through [4+2] annulation-rearrangement-aromatization from styrenes under mild conditions. The electrolysis does not require metals, oxidants and high valence substrates, indicating the atom and step-economy ideals. The dehydrodimer produced through [4+2] cycloaddition of 4-methoxy α-methyl styrene is isolated and proved to be the key intermediate for the following oxydehydrogenation to form carbon cation, which undergoes rearrangement-aromatization to afford the final products. This reaction represents a powerful access to construct multi-substituted naphthalene blocks in a single step.