Reactivity of the phosphaethynolate anion with stabilized carbocations: mechanistic studies and synthetic applications.
Chem Sci
; 2024 Aug 08.
Article
em En
| MEDLINE
| ID: mdl-39165734
ABSTRACT
The reactivity of sodium phosphaethynolate Na(OCP) towards various Mayr's reference electrophiles was investigated using conventional UV-visible and laser-flash photolysis techniques. The kinetic data, along with density functional theory (DFT) calculations, enabled the first experimental quantification of the phosphorus nucleophilicity of [OCP]-. Product studies of these reactions demonstrate the formation of secondary as well as tertiary phosphines. The mechanism of this unprecedented phosphorus-atom transfer reaction is thoroughly discussed, with key intermediates successfully isolated and characterized. Importantly, some bulky secondary phosphine oxides synthesized using this approach, have demonstrated high efficiency as ligands in the Suzuki coupling reaction.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Chem Sci
Ano de publicação:
2024
Tipo de documento:
Article