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Unveiling the Phosphine-Mediated N-Transfer from Azide to Isocyanide en Route to Carbodiimides and
Aurelia Pastor1, Carmen Lopez-Leonardo1, Guillermo Cutillas-Font1
1Departamento de Química Orgánica, Facultad de Química, Regional Campus of International Excellence "Campus Mare Nostrum", Universidad de Murcia, E-30100Murcia, Spain.
Abstract:
Intramolecular reactions between isocyano and iminophosphorane functions yield species containing an embedded 1,3,2-diazaphosphetidine ring, as result of the [2 + 2] cycloaddition of the primary reactive product, the cyclic carbodiimide, with a second unit of reactant. DFT studies reveal a first rate-determining step entailing a [2 + 1] cycloaddition involving the isocyanide carbon atom and the P═N double bond, with the further intervention of a dipolar precursor of the intermediate carbodiimide. The 1,3,2-diazaphosphetidine ring of the final products is shown to be hydrolytically and thermally labile.
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