Hindered aryl bromides for regioselective palladium-catalysed direct arylation at less favourable C5-carbon of 3-substituted thiophenes

Jin, Rongwei; Bheeter, Charles Beromeo; Doucet, Henri

doi:10.3762/bjoc.10.123

Cited by 12 publications

(5 citation statements)

References 31 publications

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“…For example, the coupling of 2-bromo-1,3-dichlorobenzene with 3-chloro-, 3-acetyl-or 3-methyl-thiophenes afforded, in all cases, C5-arylated products (Scheme 22). 100…”

Section: C2-or C5-arylation Of 3-substituted Thiophenesmentioning

confidence: 99%

Regioselectivity in palladium-catalysed direct arylation of 5-membered ring heteroaromatics

Bheeter

Chen

Soulé

2016

Catal. Sci. Technol.

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207

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International audienceIn recent years, palladium-catalyzed arylation of heteroaroms. via C-H bond activation has become a popular method for generating carbon-carbon bonds. For this reaction, a wide variety of heteroaroms. such as (benzo)furans, (benzo)thiophenes, pyrroles, indoles, thiazoles, oxazoles, imidazoles, pyrazoles or triazoles can be employed. In most of these heterocycles, several reactive C-H bonds are present. If specific C-H bonds of such heteroarenes can be coupled with arenes, this becomes one of the most simple methods to access bi(hetero)arenes. In the past few years, several results using modified and improved catalysts and new reaction conditions have been reported permitting better control of the regioselectivity of such arylations. For example, initially only C2- or C5-arylated thiophenes were accessible via palladium-catalyzed direct arylation, whereas now regioselective C3- or C4-arylations are possible when appropriate reaction conditions are used. In this review, the influence of the reactants, catalysts and reaction conditions on the regioselectivity of palladium-catalyzed arylation of heteroaroms. is reported. The recent progress in the regioselectivity control now allows the synthesis of a wide variety of complex mols. using only a few steps, and will certainly provide simpler access to new heteroaryl derivs. in the next years

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“…For example, the coupling of 2-bromo-1,3-dichlorobenzene with 3-chloro-, 3-acetyl-or 3-methyl-thiophenes afforded, in all cases, C5-arylated products (Scheme 22). 100…”

Section: C2-or C5-arylation Of 3-substituted Thiophenesmentioning

confidence: 99%

Regioselectivity in palladium-catalysed direct arylation of 5-membered ring heteroaromatics

Bheeter

Chen

Soulé

2016

Catal. Sci. Technol.

Self Cite

207

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“…The use of congested 2‐bromo‐1,3‐dichlorobenzene as the coupling partner also allowed to control the regioselectivity of the arylation of 3‐substituted thiophene derivatives in favor of the C5‐position [37] . For example, the coupling of 2‐bromo‐1,3‐dichlorobenzene with thiophenes bearing chloro, acetyl or methyl at C3‐position afforded regioselectively in all cases the C5‐arylated thiophenes (Scheme 19).…”

Section: Steric Hindrancementioning

confidence: 99%

Effective Tools for the Metal‐Catalyzed Regiodivergent Direct Arylations of (Hetero)arenes

Huang

Benzai

Shi

et al. 2020

The Chemical Record

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The direct functionalization of two different C−H bonds of the same organic molecule using different procedures ‐ also called regiodivergent C−H bond functionalization ‐ currently represents an important research topic in organic chemistry, as it demonstrates the versatility of C−H bond functionalization methodology. Over the last decade, the number of tools to control such regiodivergent C−H bond functionalizations has increased significantly. In this account, we will present the various tools that allowed us to arylate different positions of various (hetero)arenes, via a C−H bond functionalization, using palladium or ruthenium catalysis.

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“…We decided to explore further the phosphine-free procedure because it offers several potential advantages that make it particularly attractive: [54,55] 1) it is efficient for an electron-deficient aryl bromide such as diBrBz, 2) it needs neither phosphine ligand nor additive and 3) it uses a small amount of catalyst. Moreover, we highlight the fact that this reaction is rather clean: mostly the target molecule 1, the bis-adduct 2 and molecule 3 arising from the 5,5′-homocoupling of ThCHO were present in significant amounts in the crude along with the unreacted starting reactants diBrBz and ThCHO (see the NMR spectra in the Supporting Information).…”

Section: Direct Arylationmentioning

confidence: 99%

Dissymmetrization of Benzothiadiazole by Direct C–H Arylation: A Way to Symmetrical and Unsymmetrical Elongated π‐Conjugated Molecules

et al. 2017

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5‐(7‐Bromo‐2,1,3‐benzothiadiazol‐4‐yl)‐2‐thiophenecarbaldehyde is a small building block of great interest for its use in the elaboration of symmetrical or unsymmetrical donor–acceptor π‐conjugated molecules for optoelectronic applications. Herein, a convenient, one‐pot, two‐component synthesis of this intermediate is reported, based upon a palladium‐catalysed, phosphine‐ and additive‐free, direct C–H arylation process. The synthesis has been studied in depth to obtain optimum yields and selectivity by an efficient and environmentally friendly strategy for sustainable synthesis.

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Hindered aryl bromides for regioselective palladium-catalysed direct arylation at less favourable C5-carbon of 3-substituted thiophenes

Cited by 12 publications

References 31 publications

Regioselectivity in palladium-catalysed direct arylation of 5-membered ring heteroaromatics

Regioselectivity in palladium-catalysed direct arylation of 5-membered ring heteroaromatics

Effective Tools for the Metal‐Catalyzed Regiodivergent Direct Arylations of (Hetero)arenes

Dissymmetrization of Benzothiadiazole by Direct C–H Arylation: A Way to Symmetrical and Unsymmetrical Elongated π‐Conjugated Molecules

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