Tandem Oxidative C-H Amination and Iodization to Synthesize Difunctional Atropoisomeric P-Stereogenic Phosphinamides.

An efficient metal-free tandem intramolecular oxidative C-H amination and iodization of phosphinamide was performed and a series of new phosphorus heterocyclic compounds was obtained. This method provides a concise and highly valuable pathway for the synthesis of difunctional atropoisomeric P-stereogenic phosphinamides.

Dithienophosphole-Based Phosphinamides with Intriguing Self-Assembly Behavior.

A new, highly adaptable type of phosphinamide-based hydrogen bonding is representatively demonstrated in π-conjugated phosphole materials. The rotational flexibility of these intermolecular P=O-H-N hydrogen bonds is demonstrated by X-ray crystallography and variable-concentration NMR spectroscopy. In addition to crystalline compounds, phosphinamide hydrogen bonding was successfully introduced into the self-assembly of soft crystals, liquid crystals, and organogels, thus highlighting the high general value of this type of interaction for the formation of organic soft materials.

Efficient asymmetric synthesis of structurally diverse P-stereogenic phosphinamides for catalyst design.

The use of chiral phosphinamides is relatively unexplored because of the lack of a general method for the synthesis. Reported herein is the development of a general, efficient, and highly enantioselective method for the synthesis of structurally diverse P-stereogenic phosphinamides. The method relies on nucleophilic substitution of a chiral phosphinate derived from the versatile chiral phosphinyl transfer agent 1,3,2-benzoxazaphosphinine-2-oxide. These chiral phosphinamides were utilized for the first synthesis of readily tunable P-stereogenic Lewis base organocatalysts, which were used successfully for highly enantioselective catalysis.