[​4+2] versus [​2+2] Homodimerization in P(V) Derivatives of 2,4-Disubstituted Phospholes

Guillaume Bousrez (1) , Emmanuel Nicolas (2) , Agathe Martinez (1) , Sylviane Chevreux (1) , Florian Jaroschik (1)

1 ICMR - Institut de Chimie Moléculaire de Reims - UMR 7312
2 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)

Phosphole P(V) derivatives are interesting building blocks for various applications from ligand synthesis to material sciences. We herein describe the preparation and characterisation of new 2,4-disubstituted oxo-, thiooxo-, and selenooxophospholes. The nature of the substituents on the phosphole ring determines the reactivity of these compounds towards homodimerization reactions. Aryl and trimethylsilyl substituted oxophospholes undergo selective [4+2] dimerization, whereas, for thiooxo-and selenooxophospholes, light-induced, selective [2+2] head-to-head dimerization occurs in the case of aryl substituents. DFT calculations provide some insights on these differences in reactivity.

Domains: Organic chemistry

Guillaume Bousrez, Emmanuel Nicolas, Agathe Martinez, Sylviane Chevreux, Florian Jaroschik. [​4+2] versus [​2+2] Homodimerization in P(V) Derivatives of 2,4-Disubstituted Phospholes. Heteroatom Chemistry, 2019, 2019, pp.2596405. ⟨10.1155/2019/2596405⟩. ⟨cea-02092318⟩