Nickel-Catalyzed Formal Aminocarbonylation of Unactivated Alkyl Iodides with Isocyanides.

Herein, we disclose a Ni-catalyzed formal aminocarbonylation of primary and secondary unactivated aliphatic iodides with isocyanides to afford alkyl amide, which proceeds via the selective monomigratory insertion of isocyanides with alkyl iodides, subsequent ß-hydride elimination, and hydrolysis process. The reaction features wide functional group tolerance under mild conditions. Additionally, the selective, one-pot hydrolysis of reaction mixture under acid conditions allows for expedient synthesis of the corresponding alkyl carboxylic acid.

Nickel-catalyzed allylic carbonylative coupling of alkyl zinc reagents with tert-butyl isocyanide.

Transition metal-catalyzed carbonylation with carbon nucleophiles is one of the most prominent methods to construct ketones, which are highly versatile motifs prevalent in a variety of organic compounds. In comparison to the well-established palladium catalytic system, the nickel-catalyzed carbonylative coupling is much underdeveloped due to the strong binding affinity of CO to nickel. By leveraging easily accessible tert-butyl isocyanide as the CO surrogate, we present a nickel-catalyzed allylic carbonylative coupling with alkyl zinc reagent, allowing for the practical and straightforward preparation of synthetically important ß,γ-unsaturated ketones in a linear-selective fashion with excellent trans-selectivity under mild conditions. Moreover, the undesired polycarbonylation process which is often encountered in palladium chemistry could be completely suppressed. This nickel-based method features excellent functional group tolerance, even including the active aryl iodide functionality to allow the orthogonal derivatization of ß,γ-unsaturated ketones. Preliminary mechanistic studies suggest that the reaction proceeds via a π-allylnickel intermediate.

Facile Synthesis of Nitrogen-Containing Six-Membered Benzofuzed Phenophosphazinine Oxides and Studies of the Photophysical Properties.

A facile synthesis of nitrogen-containing six-membered benzofuzed phosphacycles has been described. This cyclization reaction triggered by Tf2O provides an expedient protocol of phosphacycles with a simple operation at mild conditions. The preliminary photophysical studies of these novel materials reveal that the fluorescence intensity enhances with the molecular aggregation in the solid state and that the introduction of the sterically bulky phenanthrene group into the phosphacycles allows a significant increase in the fluorescence quantum yield.