Palladium-catalyzed stereospecific C–P coupling toward diverse PN-heterocycles

Abstract

<h2>Summary</h2> Phosphorous-containing heterocycles have attracted particular interest because they exhibit markedly different properties than common oxygen-, nitrogen-, and/or sulfur-based heterocyclic compounds. However, the study of such molecules remains difficult because of a lack of synthetic methods with which to synthesize them, especially with respect to the construction of P-stereogenic centers. Here, we present a simple, versatile method for the synthesis of PN-heterocycles bearing P(V) centers from phosphanamines through palladium-catalyzed intramolecular C–P coupling. Under the developed catalytic systems, chiral PN-heterocycles can be produced from P(III)-stereogenic precursors without loss of stereochemical integrity. Computational studies revealed the detailed reaction pathway and the origin of stereospecificity. The methods showed excellent functional-group tolerance, allowing access to diverse, optoelectronically relevant products that are stable under air and moisture.