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- ItemOn the Reactivity of Phosphaalumenes towards C−C Multiple Bonds(Weinheim : Wiley-VCH, 2023) Nees, Samuel; Wellnitz, Tim; Dankert, Fabian; Härterich, Marcel; Dotzauer, Simon; Feldt, Milica; Braunschweig, Holger; Hering‐Junghans, ChristianHeterocycles containing group 13 and 15 elements such as borazines are an integral part of organic, biomedical and materials chemistry. Surprisingly, heterocycles containing P and Al are rare. We have now utilized phosphaalumenes in reactions with alkynes, alkenes and conjugated double bond systems. With sterically demanding alkynes 1,2-phosphaalumetes were afforded, whereas the reaction with HCCH or HCCSiMe3 gave 1,4-phosphaaluminabarrelenes. Using styrene saturated 1,2-phosphaalumates were formed, which reacted further with additional styrene to give different regio-isomers of 1,4-aluminaphosphorinanes. Using ethylene, a 1,4-aluminaphosphorinane is obtained, while with 1,3-butadiene a bicyclic system containing an aluminacyclopentane and a phosphirane unit was synthesized. The experimental work is supported by theoretical studies to shed light on the mechanism governing the formation of these heterocycles.