The reactivity of acyl chlorides towards sodium phosphaethynolate, Na(OCP): a mechanistic case study† †Electronic supplementary information (ESI) available. CCDC 986673, 1454789 and 1454790. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc01269h
| Autor: | Heift, Dominikus, Benkő, Zoltán, Suter, Riccardo, Verel, René, Grützmacher, Hansjörg |
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| Jazyk: | angličtina |
| Rok vydání: | 2016 |
| Předmět: | |
| Zdroj: | Chemical Science |
| ISSN: | 2041-6539 2041-6520 |
| Popis: | The phosphaethynolate anion (OCP)– has three different functions in the reaction with 2,4,6-trimethylbenzoyl chloride (MesCOCl): it acts as a nucleophile, as an en-component in [2 + 2] cycloadditions and as a formal P– transfer reagent. The reaction of Na(OCP) with mesitoyl chloride delivers an ester functionalized 1,2,4-oxadiphosphole in a clean and P-atom economic way. The reaction mechanism has been elucidated by means of detailed NMR-spectroscopic, kinetic and computational studies. The initially formed acyl phosphaketene undergoes a pseudo-coarctate cyclization with an (OCP)– anion under the loss of carbon monoxide to yield a five-membered ring anion. Subsequently, the nucleophilic attack of the formed heterocyclic anion on a second acyl chloride molecule results in the 1,2,4-oxadiphosphole. The transient acyl phosphaketene is conserved during the reaction in the form of four-membered ring adducts, which act as a reservoir. Consequently, the phosphaethynolate anion has three different functions in these reactions: it acts as a nucleophile, as an en-component in [2 + 2] cycloadditions and as a formal P– transfer reagent. |
| Databáze: | OpenAIRE |
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