Efficient Palladium-Catalyzed Cyclotrimerization of Arynes: Synthesis of Triphenylenes

Peña, Diego; Escudero, Sonia; Pérez, Dolores; Guitián, Enrique; Castedo, Luís

doi:10.1002/(sici)1521-3773(19981016)37:19<2659::aid-anie2659>3.0.co;2-4

Cited by 261 publications

(41 citation statements)

References 7 publications

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“…For example, Pérez et al. have reported [2+2+2] cyclotrimerization of benzynes (Scheme a) . The Larock group introduced annulation of arynes using 2‐halobiaryls .…”

Section: Methodsmentioning

confidence: 75%

“…Among the 35 parent structural units of PAHs, triphenylene belongs to a branched all‐benzoid category . Pd‐catalyzed annulation approaches to triphenylene moieties are based on aryne chemistry . For example, Pérez et al.…”

Section: Methodsmentioning

confidence: 99%

“…Cyclic diaryliodonium salts 2 b and 2 c bearing difluoro and dimethyl groups provided good yields to afford 3 ab and 3 ac , respectively. Given the difficulties in constructing a diverse array of tailored triphenylenes, arising from the planar and (un)symmetrical structures, the reaction scope of this approach is comparable to that of previously reported methods . Overall, the electronic nature of the substrates bearing amide DGs (and substituents) significantly affects the efficiency of the annulation.…”

Section: Methodsmentioning

confidence: 99%

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An Annulative Synthetic Strategy for Building Triphenylene Frameworks by Multiple C−H Bond Activations

et al. 2017

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CÀHactivation is aversatile tool for appending aryl groups to aromatic systems.H owever,h eavy demands on multiple catalytic cycle operations and site-selectivity have limited its use for graphene segment synthesis.AP d-catalyzed one-step synthesis of functionalized triphenylene frameworks is disclosed, which proceeds by 2-or 4-fold CÀHa rylation of unactivated benzene derivatives.A Pd 2 (dibenzylideneacetone) 3 catalytic system, using cyclic diaryliodonium salts as p-extending agents,l eads to site-selective inter-a nd intramolecular tandem arylation sequences.M oreover,N -substituted triphenylenes are applied to af ield-effect transistor sensor for rapid, sensitive,a nd reversible alcohol vapor detection.Scheme 1. Synthesis of triphenylene frameworks.

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“…For example, Pérez et al. have reported [2+2+2] cyclotrimerization of benzynes (Scheme a) . The Larock group introduced annulation of arynes using 2‐halobiaryls .…”

Section: Methodsmentioning

confidence: 75%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

An Annulative Synthetic Strategy for Building Triphenylene Frameworks by Multiple C−H Bond Activations

et al. 2017

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“…In particular, the recent aryne-based chemistry has made great advances in synthetic chemistry [3][4][5][6][7][8][9][10][11][12][13][14]. Our laboratory is interested in developing domino reactions using arynes.…”

Section: Introductionmentioning

confidence: 87%

2,3,4,9-Tetrahydro-9-(3-hydroxy-1,4-dioxo-1H-dihydro-naphthalen-2-yl)-8-methoxy-3,3-dimethyl-1H-xanthen-1-one

Yoshioka

Kohtani

Miyabe

2015

Molbank

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Abstract:The title compound 2,3,4,9-tetrahydro-9-(3-hydroxy-1,4-dioxo-1H-dihydronaphthalen-2-yl)-8-methoxy-3,3-dimethyl-1H-xanthen-1-one (5) was obtained by the nucleophilic addition of 2-hydroxy-1,4-naphthoquinone (4) to 2H-chromene derivative 3, which was prepared by the domino three-component coupling reaction of aryne precursor 1 with DMF and the active methylene compound dimedone (2). The one-pot synthesis of the title compound 5 from aryne precursor 1 was also achieved.Keywords: multi-component reaction; domino reaction; arynes; heterocycles; synthesis Arynes are highly reactive and kinetically unstable intermediates for constructing multisubstituted arenes with structural diversity and complexity [1,2]. In particular, the recent aryne-based chemistry has made great advances in synthetic chemistry [3][4][5][6][7][8][9][10][11][12][13][14]. Our laboratory is interested in developing domino reactions using arynes. We have recently developed the efficient insertion of arynes, generated in situ from ortho-(trimethylsilyl)aryl triflates and the fluoride ion, into the C=O π-bond of DMF [15][16][17][18][19][20].Synthetic strategies involving domino processes offer the advantage of multiple carbon-carbon and/or carbon-heteroatom bond formations in a single operation [21,22]. In this paper, we report two synthetic methods for preparing the title compound 5 via a domino multicomponent coupling reaction starting from the generation of an aryne. Moreover, this molecule 5 has a pharmaceutically important structure, because a similar type of compound was studied as a neuropeptide Y Y5 receptor antagonist by Merck-Banyu researchers [23]. OPEN ACCESS

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“…In the synthetic research field of aryl‐aryl coupling using the condition of CsF and Pd catalyst, Diego Peña and co‐workers carried out a systematic investigation and achieved several milestones. In 1998, Diego Peña and co‐workers reacted 1 with anhydrous CsF and palladium catalyst (tetrakis(triphenylphosphine)palladium(0) [Pd(PPh 3 ) 4 ]) and obtained triphenylene 3 via [2+2+2] cycloaddition reaction . In this process, the aryne was generated “in‐suit” in the presence of the Pd catalyst as shown in Scheme .…”

Section: General Methods Of Synthesizing Benzocyclotrimersmentioning

confidence: 99%

Synthesis of π‐Conjugated Benzocyclotrimers

Guo

Xia

Yang

et al. 2019

The Chemical Record

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Polycyclic aromatic hydrocarbons (PAHs), especially three branchphene benzocyclotrimers represent a series of molecules with intriguing physical and chemical properties. Benzocyclotrimers are also important precursors to construct fullerenes and graphenes. In this article, we review the recent progress in the preparation methods of p-conjugated benzocyclotrimers. In particular, cyclotrimerization reactions to construct varying shaped and edged benzocyclotrimers are illustrated. Various typical characterization methods for these materials, such as variable-temperature 1 H-NMR, single crystal X-ray analysis, density functional theory (DFT) calculations and atomic force microscope (AFM) measurements are included for discussion.

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Efficient Palladium-Catalyzed Cyclotrimerization of Arynes: Synthesis of Triphenylenes

Abstract: Found at the core of many discotic liquid crystals, triphenylenes can now be synthesized efficiently by the palladium-catalyzed trimerization of arynes, including those containing donor and acceptor substituents [Eq. (a); R=OMe, F].

Cited by 261 publications

References 7 publications

An Annulative Synthetic Strategy for Building Triphenylene Frameworks by Multiple C−H Bond Activations

An Annulative Synthetic Strategy for Building Triphenylene Frameworks by Multiple C−H Bond Activations

2,3,4,9-Tetrahydro-9-(3-hydroxy-1,4-dioxo-1H-dihydro-naphthalen-2-yl)-8-methoxy-3,3-dimethyl-1H-xanthen-1-one

Synthesis of π‐Conjugated Benzocyclotrimers

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