Reversible Oxidative Addition of Nonactivated C-H Bonds to Structurally Constrained Phosphenium Ions.
J Am Chem Soc
; 145(44): 24184-24190, 2023 Nov 08.
Article
in En
| MEDLINE
| ID: mdl-37877607
ABSTRACT
A series of structurally constrained phosphenium ions based on pyridinylmethylamidophenolate scaffolds are shown to undergo P(III)/P(V) oxidative addition with C-H bonds of alkynes, alkenes, and arenes. Nonactivated substrates such as benzene, toluene, and deactivated chlorobenzene are phosphorylated in quantitative yields. Computational and spectroscopic studies suggest a low-barrier isomerization from a bent to a T-shaped isomer that initiates a phosphorus-ligand-cooperative pathway and subsequent ring-chain tautomerism. Remarkably, C-H bond activations occur reversibly, allowing for reductive elimination back to P(III) at elevated temperatures or the exchange with other substrates.
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01-internacional
Database:
MEDLINE
Language:
En
Journal:
J Am Chem Soc
Year:
2023
Document type:
Article
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