Three-Step Synthesis of Fluoranthenes through Pd-Catalyzed Inter- and Intramolecular C–H Arylation

Yamaguchi, Miyuki; Higuchi, Mayu; Tazawa, Kanae; Manabe, Kei

doi:10.1021/acs.joc.6b00553

Cited by 34 publications

(30 citation statements)

References 44 publications

(61 reference statements)

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“…A c c e p t e d m a n u s c r i p t In 2016, Manabe and co-workers described a three-steps synthetic method for the preparation of fluoranthenes, involving Miura's intermolecular C−H bond arylation, nonaflation, and 5membered ring intramolecular C−H bond cyclization (Scheme 11). 33 In order to introduce an aryl group at the C8 position of 1-naphthols, they employed the conditions described by Miura for the C−H bond arylation of with halobenzenes, 34 i.e., 2.5 mol% of Pd(OAc)2 as catalyst and Cs2CO3 as base in DMF at 110 ºC. For less reactive aryl bromides, they employed PdCl2(PCy3)2 as catalyst.…”

Section: %mentioning

confidence: 99%

Application of Palladium-Catalyzed C(sp2)–H Bond Arylation to the Synthesis of Polycyclic (Hetero)Aromatics

Hagui

Doucet

2019

Chem

112

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Recently, the use of the palladium-catalyzed inter-and/or intra-molecular C-H bond arylations in the building of various π-extended (hetero)aromatic structures has emerged as a suitable alternative to the previous multi-steps synthesis. Such new methodology even allowed to prepare unprecedented π-extended molecules owing a perfect control of the reaction sites. This review gives an overview of various synthesis of Polycyclic Aromatic Hydrocarbons (PAHs) and PolyCyclic Heteroaromatics (PCHs) with planar, bowl-shaped, and helical structures prepared in high efficiency and selectivity via Pd-catalyzed C-H bond arylations. Bigger Picture Recently, π-extended compounds such as Polycyclic Aromatic Hydrocarbons (PAHs) and PolyCyclic Heteroaromatics (PCHs) have found important applications in the preparation of optoelectronic devices. The degree of π-extension, the topology of the ring fusion, and the periphery of such molecules are essential factors to control their electronic properties at a molecular level. The traditional approach to prepare nanographenes and heteroatom-doped nanographenes relies on Scholl reaction. However, such methodology suffers from limitations such as functional group compatibility. Catalysis plays a pivotal role in the discovery of new transformations enabling the synthesis of novel molecules, including organic materials. Among various catalytic transformations, Pd-catalyzed C-H bond arylation has emerged as an important tool for the construction of well-decorated polycyclic (hetero)aromatic molecules. Such direct approaches have a considerable impact on the synthesis of PAHs and PCHs by shortening the synthetic scheme and also providing a momentous opportunity to design novel structures. eTOC Blurb: This review highlights the potential of Pd-catalyzed C-H bond arylation for the synthesis of π-extended compounds that include

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Section: %mentioning

confidence: 99%

Application of Palladium-Catalyzed C(sp2)–H Bond Arylation to the Synthesis of Polycyclic (Hetero)Aromatics

Hagui

Doucet

2019

Chem

112

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“…Since this work, naphthols have been used by different groups to functionalize the C8‐position. In 2016, Manabe's team combined palladium catalyzed C8‐arylation of naphthols with an intra‐molecular C−H arylation to obtain fluoranthenes 6 in three steps which constitutes a fast method for the synthesis of polycyclic aromatic hydrocarbons (Scheme ) . Very recently, Spiewak and Weix reported a similar arylation reaction using a Ru(II) catalyst which allowed the introduction of heteroaryl groups …”

Section: C8‐functionalization Of Naphthalene Derivativesmentioning

confidence: 99%

Regioselective C−H Functionalization of Naphthalenes: Reactivity and Mechanistic Insights

Prévost

2020

ChemPlusChem

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Naphthalene is a very important skeleton in chemistry as evidenced by the large number of active compounds that contain it. For this reason, methods that can achieve easy functionalization of naphthalene derivatives are of great importance. This Minireview summarizes reactions that allow regioselective functionalization of 1‐substituted naphthalenes based on directed C−H activation strategies. Indeed, over the past ten years, many research groups have tried to develop new methodologies to directly introduce different functional groups on every position of naphthalene. In addition to the possible reactions reported in the literature, special attention has been paid to mechanistic aspects in order to explain the observed regioselectivities.

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“…9 More recently, Manabe and co-workers developed an elegant Pd-catalyzed method that enables the three-step synthesis of fluoranthenes via inter- and intramolecular C–H arylation reactions. 10 During the course of our studies on 1,8-diarylnaphthalenes, we have observed that monoaryl as well as symmetrical and unsymmetrical diarylnaphthalenes could be obtained selectively via Suzuki–Miyaura reaction using a tetrakis(triphenylphosphine)palladium (0) (Pd(PPh 3 ) 4 ) catalyst starting from 1,8-diiodonaphthalene ( 5 ). On the other hand, using a more active Pd catalyst, Pd(dppf)Cl 2 led to the formation of significant amounts of fluoranthene side products, which prompted us to investigate this transformation in detail.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Fluoranthene Derivatives via Tandem Suzuki–Miyaura and Intramolecular C–H Arylation Reactions under Both Homogeneous and Heterogeneous Catalytic Conditions

Pal¹,

Metin

Türkmen³

2017

ACS Omega

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A catalytic method for the synthesis of substituted fluoranthenes that operates via tandem Suzuki–Miyaura and intramolecular C–H arylation reactions is reported. The overall reaction sequence works effectively with homogeneous catalysis using Pd(dppf)Cl 2 as well as heterogeneous catalysis using reduced graphene oxide (rGO)-CuPd nanocatalysts with low catalyst loadings. High functional group tolerance is observed under both catalytic conditions where arylboronic acids and esters having electron-withdrawing and electron-donating substituents afforded fluoranthene products in good yields (up to 78%). Moreover, the rGO-CuPd nanocatalysts are demonstrated to be reusable by preserving almost 90% of their initial activity after the third cycle.

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Three-Step Synthesis of Fluoranthenes through Pd-Catalyzed Inter- and Intramolecular C–H Arylation

Cited by 34 publications

References 44 publications

Application of Palladium-Catalyzed C(sp2)–H Bond Arylation to the Synthesis of Polycyclic (Hetero)Aromatics

Application of Palladium-Catalyzed C(sp2)–H Bond Arylation to the Synthesis of Polycyclic (Hetero)Aromatics

Regioselective C−H Functionalization of Naphthalenes: Reactivity and Mechanistic Insights

Synthesis of Fluoranthene Derivatives via Tandem Suzuki–Miyaura and Intramolecular C–H Arylation Reactions under Both Homogeneous and Heterogeneous Catalytic Conditions

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