An Iron-Catalyzed Route to Dewar 1,3,5-triphosphabenzene and Subsequent Reactivity

Adam N. Barrett; Martin Diefenbach; Mary F. Mahon; Vera Krewald; Ruth L. Webster

doi:10.1002/ange.202208663

An Iron-Catalyzed Route to Dewar 1,3,5-triphosphabenzene and Subsequent Reactivity

Adam N. Barrett, Martin Diefenbach, Mary F. Mahon, Vera Krewald, Ruth L. Webster

Technische Universität Darmstadt

Research output: Contribution to journal › Article › peer-review

2 Citations (SciVal)

Abstract

The application of an alkyne cyclotrimerization regime with an [Fe(salen)] ₂-μ-oxo (1) catalyst to triphenylmethylphosphaalkyne (2) yields gram-scale quantities of 2,4,6-tris(triphenylmethyl)-Dewar-1,3,5-triphosphabenzene (3). Bulky lithium salt LiHMDS facilitates a rearrangement of 3 to the 1,3,5-triphosphabenzene valence isomer (3′), which subsequently undergoes an intriguing phosphorus migration reaction to form the ring-contracted species (3′′). Density functional theory calculations provide a plausible mechanism for this rearrangement. Given the stability of 3, a diverse array of unprecedented transformations was investigated. We report novel crystallographically characterized products of successful nucleophilic/electrophilic addition and protonation/oxidation reactions.

Original language	English
Article number	e202208663
Journal	Angewandte Chemie International Edition
Volume	61
Issue number	37
Early online date	9 Aug 2022
DOIs	https://doi.org/10.1002/ange.202208663
Publication status	Published - 12 Sept 2022

Bibliographical note

Engineering and Physical Sciences Research Council (Grant number(s): EP/P024254/1; Grant recipient(s): Ruth L. Webster, Adam N. Barrett);
Leverhulme Trust (Grant number(s): RPG-2020-3

Keywords

Electrophilic Addition
Iron
Nucleophilic Addition
Phosphorus Heterocycles
Reaction Mechanisms

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/ange.202208663Licence: CC BY

Cite this

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title = "An Iron-Catalyzed Route to Dewar 1,3,5-triphosphabenzene and Subsequent Reactivity",

abstract = "The application of an alkyne cyclotrimerization regime with an [Fe(salen)] 2-μ-oxo (1) catalyst to triphenylmethylphosphaalkyne (2) yields gram-scale quantities of 2,4,6-tris(triphenylmethyl)-Dewar-1,3,5-triphosphabenzene (3). Bulky lithium salt LiHMDS facilitates a rearrangement of 3 to the 1,3,5-triphosphabenzene valence isomer (3′), which subsequently undergoes an intriguing phosphorus migration reaction to form the ring-contracted species (3′′). Density functional theory calculations provide a plausible mechanism for this rearrangement. Given the stability of 3, a diverse array of unprecedented transformations was investigated. We report novel crystallographically characterized products of successful nucleophilic/electrophilic addition and protonation/oxidation reactions.",

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note = "Engineering and Physical Sciences Research Council (Grant number(s): EP/P024254/1; Grant recipient(s): Ruth L. Webster, Adam N. Barrett); Leverhulme Trust (Grant number(s): RPG-2020-3",

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doi = "10.1002/ange.202208663",

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AU - Barrett, Adam N.

AU - Diefenbach, Martin

AU - Mahon, Mary F.

AU - Krewald, Vera

AU - Webster, Ruth L.

N1 - Engineering and Physical Sciences Research Council (Grant number(s): EP/P024254/1; Grant recipient(s): Ruth L. Webster, Adam N. Barrett); Leverhulme Trust (Grant number(s): RPG-2020-3

PY - 2022/9/12

Y1 - 2022/9/12

N2 - The application of an alkyne cyclotrimerization regime with an [Fe(salen)] 2-μ-oxo (1) catalyst to triphenylmethylphosphaalkyne (2) yields gram-scale quantities of 2,4,6-tris(triphenylmethyl)-Dewar-1,3,5-triphosphabenzene (3). Bulky lithium salt LiHMDS facilitates a rearrangement of 3 to the 1,3,5-triphosphabenzene valence isomer (3′), which subsequently undergoes an intriguing phosphorus migration reaction to form the ring-contracted species (3′′). Density functional theory calculations provide a plausible mechanism for this rearrangement. Given the stability of 3, a diverse array of unprecedented transformations was investigated. We report novel crystallographically characterized products of successful nucleophilic/electrophilic addition and protonation/oxidation reactions.

AB - The application of an alkyne cyclotrimerization regime with an [Fe(salen)] 2-μ-oxo (1) catalyst to triphenylmethylphosphaalkyne (2) yields gram-scale quantities of 2,4,6-tris(triphenylmethyl)-Dewar-1,3,5-triphosphabenzene (3). Bulky lithium salt LiHMDS facilitates a rearrangement of 3 to the 1,3,5-triphosphabenzene valence isomer (3′), which subsequently undergoes an intriguing phosphorus migration reaction to form the ring-contracted species (3′′). Density functional theory calculations provide a plausible mechanism for this rearrangement. Given the stability of 3, a diverse array of unprecedented transformations was investigated. We report novel crystallographically characterized products of successful nucleophilic/electrophilic addition and protonation/oxidation reactions.

KW - Electrophilic Addition

KW - Iron

KW - Nucleophilic Addition

KW - Phosphorus Heterocycles

KW - Reaction Mechanisms

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U2 - 10.1002/ange.202208663

DO - 10.1002/ange.202208663

M3 - Article

SN - 1433-7851

VL - 61

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 37

M1 - e202208663

ER -

An Iron-Catalyzed Route to Dewar 1,3,5-triphosphabenzene and Subsequent Reactivity

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

EC Fellowship - Cast Iron Catalysis: New Protocols for the Synthesis of Carbon-Phosphorus Bonds

Cite this

An Iron-Catalyzed Route to Dewar 1,3,5-triphosphabenzene and Subsequent Reactivity

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Projects

EC Fellowship - Cast Iron Catalysis: New Protocols for the Synthesis of Carbon-Phosphorus Bonds

Cite this