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Article Dans Une Revue Journal of Organic Chemistry Année : 2020

Cyclopropenylidenephosphoranes: Rearrangement to Azetidinylidene-Methylphosphoniums

Résumé

Attempts at preparing cyclopropenylphosphonium salts by P-quaternization of α-aminophosphines with bisdiisopropylaminocyclopropenium tetrafluoroborate led to azetidin-2-ylidene methylphosphoniums as unexpected isomers, in 57-85 % yield. The basic structure of the products is discussed on the basis of X-ray crystallography analysis. The unprecedented 3→4 ring expansion process is argued to be driven by an ambivalent aromatic vs anti-aromatic character (or loss of aromaticity) of the primary phosphonium product. On the basis of DFT calculations, a mechanism involving a concerted 1,4-hydride shift/electrocyclization process as the rate determining step is proposed and discussed vs possible alternatives.
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Dates et versions

hal-02612895 , version 1 (19-05-2020)

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Citer

Clève Dionel Mboyi, Albert Poater, Jordi Poater, Carine Guyard-Duhayon, Rémi Chauvin. Cyclopropenylidenephosphoranes: Rearrangement to Azetidinylidene-Methylphosphoniums. Journal of Organic Chemistry, 2020, 85 (11), pp.7452-7458. ⟨10.1021/acs.joc.0c00847⟩. ⟨hal-02612895⟩
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