Direct Arylation of Benzo[<i>b</i>]furan and Other Benzo‐Fused Heterocycles

Dao‐Huy, Toan; Haider, Maximilian; Glatz, Fabian; Schnürch, Michael; Mihovilovic, Marko D.

doi:10.1002/ejoc.201403125

Cited by 51 publications

(29 citation statements)

References 115 publications

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“…This considerable discrepancy in performance with different functionalization of the two reactants could primarily be caused by a hydrodehalogenation side reaction . This side reaction has previously been observed in direct arylations and was often overcome by adopting different experimental conditions; however, in our study, modifying the functionalization by moving the bromine substituent from pentafluorobenzene to 2‐hexylthiophene was the best solution for reducing this side reaction. In Pd‐catalyzed coupling reactions of heterocycles, hydrodehalogenation is often a consequence of an inefficacious trans‐metalation step .…”

Section: Resultsmentioning

confidence: 66%

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Influence of functionality on direct arylation of model systems as a route toward fluorinated copolymers via direct arylation polymerization (DArP)

Livi¹,

Gobalasingham²,

Bundgaard

et al. 2015

J. Polym. Sci., Part A: Polym. Chem.

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A screening of direct arylation conditions on a model small molecule system is carried out to develop suitable conditions for the direct arylation polymerization (DArP) of fluorinated copolymers, which are incompatible with conditions previously utilized successfully for nonfluorinated systems. The model system features a coupling between a 2‐substituted thiophene and a pentafluorobenzene, where one of the partners was brominated. A substantial difference in reactivity is observed, demonstrating that the optimal functionalization for direct arylation between a thiophene‐based donor and a highly fluorinated acceptor is a halogenated thiophene and an unfunctionalized fluorinated unit, which is opposite of typical cross coupling reactions, where the acceptor is typically halogenated. The best conditions are applied to the copolymerization of 1,2,4,5‐tetrafluorobenzene and 2,2'‐(2,5‐bis((2‐hexyldecyl)oxy)−1,4‐phenylene)dithiophene. Polymers are free of β‐defects and significant homocoupling. This work further underscores the attractive simplicity, relevance, and ease of DArP while reconfirming its broad compatibility with increasingly popular fluorinated copolymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2598–2605

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Section: Resultsmentioning

confidence: 66%

“…conditions; 63,64 however, in our study, modifying the functionalization by moving the bromine substituent from pentafluorobenzene to 2-hexylthiophene was the best solution for reducing this side reaction. In Pd-catalyzed coupling reactions of heterocycles, hydrodehalogenation is often a consequence of an inefficacious trans-metalation step.…”

Section: Articlementioning

confidence: 65%

Influence of functionality on direct arylation of model systems as a route toward fluorinated copolymers via direct arylation polymerization (DArP)

Livi¹,

Gobalasingham²,

Bundgaard

et al. 2015

J. Polym. Sci., Part A: Polym. Chem.

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“…The oxidation of benzofuran with air is not reported on in standard texts [42,43,62], or in specialized texts [74]. In fact, it seems that oxidation of this oxygen-containing compound requires the use of a catalyst to enable oxidative addition (coupling) reactions [75][76][77]. On the other hand, low temperature autoxidation of benzofuran resulted in the formation of addition products [67].…”

Section: Oxidation Of Aromatic O-heterocyclic Compoundsmentioning

confidence: 99%

Autoxidation of aromatics

Sánchez

Klerk

2018

Appl Petrochem Res

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Autoxidation is a conversion pathway that has the potential to add value to multinuclear aromatic-rich coal liquids, heavy oils and bitumens, which are typically considered low-value liquids. In particular, autoxidation of these heavy materials could lead to products that may have petrochemical values, e.g., lubricity improvers and emulsifiers. Proper assessment of an oxidative transformation to ring-open the multinuclear aromatics present in heavy feeds relies on the understanding of the fundamentals of aromatic oxidation. This work reviews the selective oxidation chemistry of atoms that form part of an aromatic ring structure using oxygen (O 2) as oxidant, i.e., the oxidation of aromatic carbons as well as heteroatoms contained in an aromatic ring. Examples of industrially relevant oxidations of aromatic and heterocyclic aromatic hydrocarbons are provided. The requirements to produce oxygenates involving the selective cleavage of the ring CC bonds, as well as competing non-selective oxidation reactions are discussed. On the other hand, the Clar formalism, i.e., a rule that describes the stability of polycyclic systems, assists the interpretation of the reactivity of multinuclear aromatics towards oxidation. Two aspects are developed. First, since the interaction of oxygen with aromatic hydrocarbons depends on their structure, oxidation chemistries which are fundamentally different are possible, namely, transannular oxygen addition, oxygen addition to a carbon-carbon double bond, or free radical chemistry. Second, hydrogen abstraction is not necessary for the initiation of the oxidation of aromatics compared to that of aliphatics.

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“…Synthetic methods for assembling the benzofuran scaffold have typically involved acid-catalyzed cyclizations [11][12][13][14][15][16][17], carbonylative cyclizations via Sonogashira reactions [18][19][20][21][22][23][24], Heck-type cyclizations [25][26][27][28][29], photocyclizations [30][31][32][33][34], radical cyclizations [35][36][37][38][39], and other types of transition-metal catalyzed transformations [40][41][42][43][44][45]. When it comes to the functionalization of the furan part, there exists a considerable number of methods for directly functionalizing either the C2 or C3 position [46][47][48][49][50][51][52][53][54][55][56]. Of these two positions, C2 is generally easier to functionalize as it is significantly more reactive than C3…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Elaborate Benzofuran-2-Carboxamide Derivatives through a Combination of 8-Aminoquinoline Directed C–H Arylation and Transamidation Chemistry

et al. 2020

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Herein, we present a short and highly modular synthetic route that involves 8-aminoquinoline directed C–H arylation and transamidation chemistry, and which enables access to a wide range of elaborate benzofuran-2-carboxamides. For the directed C–H arylation reactions, Pd catalysis was used to install a wide range of aryl and heteroaryl substituents at the C3 position of the benzofuran scaffold in high efficiency. Directing group cleavage and further diversification of the C3-arylated benzofuran products were then achieved in a single synthetic operation through the utilization of a one-pot, two-step transamidation procedure, which proceeded via the intermediate N-acyl-Boc-carbamates. Given the high efficiency and modularity of this synthetic strategy, it constitutes a very attractive method for generating structurally diverse collections of benzofuran derivatives for small molecule screening campaigns.

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Direct Arylation of Benzo[b]furan and Other Benzo‐Fused Heterocycles

Cited by 51 publications

References 115 publications

Influence of functionality on direct arylation of model systems as a route toward fluorinated copolymers via direct arylation polymerization (DArP)

Influence of functionality on direct arylation of model systems as a route toward fluorinated copolymers via direct arylation polymerization (DArP)

Autoxidation of aromatics

Synthesis of Elaborate Benzofuran-2-Carboxamide Derivatives through a Combination of 8-Aminoquinoline Directed C–H Arylation and Transamidation Chemistry

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