Unveiling the Phosphine-Mediated <i>N</i>-Transfer from Azide to Isocyanide en Route to Carbodiimides and 4-Imino-1,3,2-diazaphosphetidines
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.
Authors
- Guillermo Cutillas-Font (ORCID: https://orcid.org/0000-0003-2157-5594)
- Mateo Alajarı́n (ORCID: https://orcid.org/0000-0002-7112-5578)
- Carmen López‐Leonardo (ORCID: https://orcid.org/0000-0001-8737-4280)
- Alberto Martínez‐Cuezva (ORCID: https://orcid.org/0000-0001-8093-7888)
- Marta Marín‐Luna (ORCID: https://orcid.org/0000-0003-3531-6622)
- Isabel Saura‐Llamas
- José-Antonio Garcı́a-López (ORCID: https://orcid.org/0000-0002-8143-7081)
- Aurelia Pastor (ORCID: https://orcid.org/0000-0003-0437-2605)
Institutions
- Universidad de Murcia (ES)
Publication Details
- Journal
- Organic Letters
- Published
- 2024-12-21
- DOI
- https://doi.org/10.1021/acs.orglett.4c03902
- Citations
- 2
- Primary Topic
- Chemical Synthesis and Analysis
- Type
- article
- Field-Weighted Citation Impact
- 0.47
Funders
- Fundación Séneca
- Ministerio de Ciencia e Innovación
- European Regional Development Fund
- Agencia Estatal de Investigación