N2 Cleavage on d4/d4 Molybdenum Centers and Its Further Conversion into Iminophosphorane under Mild Conditions.

The synthesis of N-containing organophosphine compounds using N2 as the nitrogen source under mild conditions has attracted much attention. Herein, the conversion of N2 into iminophosphorane was reported. By visible light irradiation, N2 was split on a MoII complex bearing a PNCNP ligand, directly forming the MoV nitride. After the N-P bond formation on the terminal nitride, the N atom from N2 was ultimately transferred into iminophosphorane. Key intermediates were characterized.

Switching the Regioselectivity Access to Pyrroles and Isoquinolines from Ketoxime Acetates and Ynals.

A novel formal [3+2] and [4+2] annulation of ketoxime acetates and ynals for the synthesis of pyrroles and isoquinolines has been developed. By simply switching the catalyst and solvent, the reaction proceeds via two pathways. The reactions are achieved under mild conditions with broad substrate scope and excellent regioselectivity.

Construction of N-S and C-N Bonds from Reactions of Benzofuroxans with DMSO or THF.

Novel ring-opening reactions are achieved employing benzofuroxan as a new type of iminating or aminating reagent. These diverse transformations give access to three types of molecular scaffolds, N-aryl dimethylsulfoximines, methanesulfonamides, and hemiaminal ethers, which are important structural motifs in organic and medicinal chemistry. The procedures feature solvent-involved reactions, easily available starting materials, operational simplicity, high atom economy, and the potential further transformation of nitro group.

Catalyst-Free Annulation of 2-Pyridylacetates and Ynals with Molecular Oxygen: An Access to 3-Acylated Indolizines.

A catalyst and additive-free annulation of 2-pyridylacetates and ynals under molecular oxygen was the first developed, affording 3-acylated indolizines in good to excellent yields. Molecular oxygen was used as the source of the carbonyl oxygen atom in indolizines. This approach was compatible with a wide range of functional groups, and especially it has been successfully extended to unsaturated double bonds and triple bonds, which were difficult to prepare by previous methods in a single step.

A facile tandem decyanation/cyanation reaction of α-iminonitriles toward cyano-substituted amides.

A new tandem decyanation/cyanation reaction of α-iminonitriles has been developed. A variety of cyano-substituted aryl amides and heteroaryl amides are synthesized in good yields. Both electron-rich and electron-deficient groups are compatible with the standard conditions. This reaction features a nonmetallic cyano source, tandem decyanation and cyanation reaction, waste utilization of the HCN from the hydrolysis of α-iminonitriles, formation of two important functional groups in one-step operation, etc.

Cyanide-Free Ce(III)-Catalyzed Highly Efficient Synthesis of α-Iminonitriles from 2-Aminopyridines and Nitroalkenes via Intermolecular Dehydration Reaction.

A direct and rapid method for the synthesis of α-iminonitriles achieved good to excellent yields. A novel intermolecular dehydration reaction between 2-aminopyridines and nitroalkenes is reported via a rare-earth-metal catalyst. The merits of this transformation include cyanide-free protocol, short reaction time, simple operation, water as the only byproduct, commercially available reagents, good functional group tolerance, etc. Moreover, nitroalkenes are demonstrated as a new "CN" source in this transformation.