Synthesis of Phosphabenzenes by an Iron‐Catalyzed [2+2+2] Cycloaddition Reaction of Diynes with Phosphaalkynes

Nakajima, Kazunari; Takata, Shohei; Sakata, Ken; Nishibayashi, Yoshiaki

doi:10.1002/ange.201502531

Cited by 11 publications

(1 citation statement)

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“…Geometry calculations and checks for higher symmetry were performed with the PLATONp rogram. [42] CCDC 1484202 (7), 1575364 (8), and 1575365 (10)c ontain the supplementary crystallographic data for this paper.T hese data are provided free of charge by The Cambridge Crystallographic Data Centre.…”

Section: Methodsmentioning

confidence: 99%

2‐(Trimethylsilyl)‐λ³‐Phosphinine: Synthesis, Coordination Chemistry, and Reactivity

Habicht

Wossidlo

Bens

et al. 2017

Chemistry A European J

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The [4+2] cycloaddition reaction between 2-pyrone and Me Si-C≡P gives the corresponding 2-(trimethylsilyl)-λ -phosphinine in good yields as a rather air and moisture stable, colorless oil. Insight into the regioselectivity of the pericyclic reaction was obtained with the help of deuterium-labeling experiments. The silyl-phosphinine acts as a ligand for the preparation of a Cu(I) and the first crystallographically characterized phosphinine-Ag(I) complex. The title compound was further used as a starting material for an alternative preparation of the parent phosphinine C H P by means of protodesilylation with HCl. C H P reacts with CuBr⋅S(CH ) to give an infinite Cu(I)Br coordination polymer. DFT calculations shed light on the influence of the -Si(CH ) group on the electronic properties of the aromatic phosphorus heterocycle.

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Section: Methodsmentioning

confidence: 99%

2‐(Trimethylsilyl)‐λ³‐Phosphinine: Synthesis, Coordination Chemistry, and Reactivity

Habicht

Wossidlo

Bens

et al. 2017

Chemistry A European J

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Gold(I)‐Catalyzed Intramolecular Hydroarylation of o‐Ethynylarylphosphonium Salt Leading to the Formation of Seven‐ and Six‐membered Phosphacycles

2020

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The gold(I)-catalyzed intramolecular hydroarylation of o-ethynylarylphosphonium salt 1 gave phosphepinium 2 or phosphinium salt 3. The use of methylphosphonium salt instead of phosphine chalcogenide is key to success for the intramolecular hydroarylation. The substrate with 2-methoxyphenyl group at the alkyne position preferentially provided seven-membered phosphacycle 2, while that with a hydrogen did six-membered phosphacycle 3. Theoretical calculations revealed that the activation energy of 6-exo-dig cyclization in the substrate with the aryl group increased due to the steric repulsion of the two aryl rings. Furthermore, the Wittig-type reaction of phosphepinium salt 2 a afforded methyl-substituted phosphepin oxide 4 a via the elimination of an aryl group.

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Iron‐Catalyzed Cyclotrimerization of Terminal Alkynes by Dual Catalyst Activation in the Absence of Reductants

et al. 2017

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Catalyzing C−C bond‐forming reactions with earth‐abundant metals under mild conditions is at the heart of sustainable synthesis. The cyclotrimerization of alkynes is a valuable atom‐efficient reaction in organic synthesis that is enabled by several metal catalysts, including iron. This study reports an effective iron‐catalyzed cyclotrimerization for the regioselective synthesis of 1,2,4‐substituted arenes (1 mol % catalyst, toluene, 20 °C, 5 min). A dual activation mechanism (substrate deprotonation, reductive elimination) renders the simple FeII precatalyst highly active in the absence of any reductant.

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Synthesis of Phosphabenzenes by an Iron‐Catalyzed [2+2+2] Cycloaddition Reaction of Diynes with Phosphaalkynes

Abstract: A method for the synthesis of phosphabenzenes under iron catalysis is described. Thus, the FeI2‐catalyzed [2+2+2] cycloaddition of diynes with phosphaalkynes in m‐xylene gave a variety of phosphabenzenes in good to high yields (up to 87 % yield).

Cited by 11 publications

References 71 publications

2‐(Trimethylsilyl)‐λ³‐Phosphinine: Synthesis, Coordination Chemistry, and Reactivity

2‐(Trimethylsilyl)‐λ³‐Phosphinine: Synthesis, Coordination Chemistry, and Reactivity

Gold(I)‐Catalyzed Intramolecular Hydroarylation of o‐Ethynylarylphosphonium Salt Leading to the Formation of Seven‐ and Six‐membered Phosphacycles

Iron‐Catalyzed Cyclotrimerization of Terminal Alkynes by Dual Catalyst Activation in the Absence of Reductants

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Synthesis of Phosphabenzenes by an Iron‐Catalyzed [2+2+2] Cycloaddition Reaction of Diynes with Phosphaalkynes

Abstract: A method for the synthesis of phosphabenzenes under iron catalysis is described. Thus, the FeI2‐catalyzed [2+2+2] cycloaddition of diynes with phosphaalkynes in m‐xylene gave a variety of phosphabenzenes in good to high yields (up to 87 % yield).

Cited by 11 publications

References 71 publications

2‐(Trimethylsilyl)‐λ3‐Phosphinine: Synthesis, Coordination Chemistry, and Reactivity

2‐(Trimethylsilyl)‐λ3‐Phosphinine: Synthesis, Coordination Chemistry, and Reactivity

Gold(I)‐Catalyzed Intramolecular Hydroarylation of o‐Ethynylarylphosphonium Salt Leading to the Formation of Seven‐ and Six‐membered Phosphacycles

Iron‐Catalyzed Cyclotrimerization of Terminal Alkynes by Dual Catalyst Activation in the Absence of Reductants

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2‐(Trimethylsilyl)‐λ³‐Phosphinine: Synthesis, Coordination Chemistry, and Reactivity

2‐(Trimethylsilyl)‐λ³‐Phosphinine: Synthesis, Coordination Chemistry, and Reactivity