[3 + 2] Cycloadditions of Tertiary Amine -Oxides and Silyl Imines as an Innovative Route to 1,2-Diamines.

We have developed a one-pot synthetic method for producing 1,2-diamines from easily prepared and commercially available precursors through a formal umpolung process. Our method utilizes an efficient [3 + 2] cycloaddition as the key step in forming substituted 1,2-diamines in moderate to high yields. These resulting compounds can undergo subsequent transformations, demonstrating their utility as synthetic building blocks for more complex scaffolds.

Synthetic Exploration of Bis(phenolate) Aza-BODIPYs and Heavier Group 13 Chelates.

A series of boron, aluminum, gallium, and indium chelates containing the underexplored bis(phenolate) aza-dipyrromethene (aza-DIPY) core were prepared. These compounds were found to possess near-infrared absorption and emission profiles in the 710 to 770 nm domain and exhibit quantum yield values up to 14%. X-ray diffraction analysis revealed that heavier group 13 bis(phenolate) aza-DIPY chelates possessed octahedral geometries with either THF or pyridine groups occupying the axial positions as opposed to the tetrahedral geometry of the boron chelate.

Multi-Ion Bridged Pathway of -Oxides to 1,3-Dipole Dilithium Oxide Complexes.

Roussi's landmark work on the generation of 1,3-dipoles from tertiary amine -oxides has not reached its full potential since its underlying mechanism is neither well explored nor understood. Two competing mechanisms were previously proposed to explain the transformation involving either an iminium ion or a diradical intermediate. Our investigation has revealed an alternative mechanistic pathway that explains experimental results and provides significant insights to guide the creation of new -oxide reagents beyond tertiary alkylamines for direct synthetic transformations.