Palladium-Catalyzed Three-Component Selective Aminoallylation of Diazo Compounds

We describe a Xantphos-containing dinuclear palladium complex-enabled geminal aminoallylation of diazocarbonyl compounds, which selectively provides a range of quaternary alpha-amino esters. Direct N-H insertion, allylic alkylation of amino nucleophiles, and diene formation were not observed under standard conditions. Mechanistic studies indicated that a relayed pathway via allylation of the N-H insertion product or [2,3]-sigmatropic rearrangement of an ylide intermediate was unlikely.

Automated summary

In this study, a Xantphos-containing dinuclear palladium complex was used to catalyze the geminal aminoallylation of diazocarbonyl compounds, providing a selective synthesis of various quaternary alpha-amino esters. The reaction did not proceed through direct N-H insertion, allylic alkylation of amino nucleophiles, or diene formation. Mechanistic investigations indicated that a relayed pathway via allylation or a [2,3]-sigmatropic rearrangement was unlikely.