Reversible oxidative addition of nonactivated C-H bonds to structurally constrained phosphenium ions
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 phosphorylate...
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| Main Authors: | , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
October 25, 2023
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| In: |
Journal of the American Chemical Society
Year: 2023, Volume: 145, Issue: 44, Pages: 24184-24190 |
| ISSN: | 1520-5126 |
| DOI: | 10.1021/jacs.3c08456 |
| Online Access: | Verlag, kostenfrei, Volltext: https://doi.org/10.1021/jacs.3c08456
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| Author Notes: | Daniel Roth, Alexander T. Radosevich, and Lutz Greb |
| Summary: | 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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| Item Description: | Gesehen am 29.11.2023 |
| Physical Description: | Online Resource |
| ISSN: | 1520-5126 |
| DOI: | 10.1021/jacs.3c08456 |