Indium‐Catalyzed Heteroaryl–Heteroaryl Bond Formation through Nucleophilic Aromatic Substitution

Tsuchimoto, Teruhisa; Iwabuchi, Mami; Nagase, Yuta; Oki, Kenji; Takahashi, Hiroshi

doi:10.1002/anie.201005750

Cited by 42 publications

(19 citation statements)

References 56 publications

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“…Increasing the molar equivalent of 1 a to 2 a from 2.5 to 3 had no positive effect on the yield of 3 aa (entries 14 and 15). Reducing the amount of 1 a to 2 molar equivalents similarly provided 3 aa in a comparable yield of 63% (entry 16), but the further lower loading of 1 a (1.5 molar equivalents) slightly brought about the S N Ar biheteroaryl formation between 2 a and product 3 aa (entry 17), as in our preceding study . No amination was observed in the absence of a Lewis acid catalyst (entry 18).…”

Section: Resultsmentioning

confidence: 51%

“…On the other hand, we have disclosed the first example of the S N Ar‐based catalytic biheteroaryl synthesis by connecting two electron‐rich heteroaryl molecules . The key strategic idea of the method is that an indium Lewis acid temporarily behaves as an EWG by forming an indium−heteroaryl π‐complex, thus allowing to use heteroaryl electrophiles without having the EWGs as well as non‐metalated heteroaryl nucleophiles, in contrast to the conventional S N Ar‐based biheteroaryl synthesis.…”

Section: Introductionmentioning

confidence: 99%

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A Heteroarylamine Library: Indium‐Catalyzed Nucleophilic Aromatic Substitution of Alkoxyheteroarenes with Amines

et al. 2018

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Under indium Lewis acid catalysis, electron-rich five-membered heteroaryl electrophiles fused with/without a benzene ring were found to couple with amines to produce heteroarylamines with broad structural diversity. The heteroarylamine formation proceeds through the cleavage of a heteroarylÀOMe bond by the nucleophilic attack of the amine based on the nucleophilic aromatic substitution (S N Ar) reaction. In contrast to the corresponding traditional S N Ar amination, the present S N Ar-based heteroaryl amination can be performed without relying on both heteroaryl electrophiles with electron-withdrawing groups and nucleophilicity-enhanced metal amides. High compatibility towards the functional groups such as NO 2 , Br, I, CF 3 , CN, CO 2 Et, pyridyl, thiazolyl, C=C, and OH groups was observed, thus showing the practicality and reliability of this method. Mechanistic studies indicated that a carbonÀindium bond is likely to be formed on the heteroaryl ring during the process. Scheme 3. Indium-catalyzed S N Ar amination of 3,4-dimethoxythiophene with aniline.Scheme 4. Indium-catalyzed S N Ar amination of 3-bromo-4methoxythiophene with aniline.Scheme 5. Indium-catalyzed tandem S N Ar reaction of 2methoxythiophene with N-methyl-p-toluidine.

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Section: Resultsmentioning

confidence: 51%

Section: Introductionmentioning

confidence: 99%

A Heteroarylamine Library: Indium‐Catalyzed Nucleophilic Aromatic Substitution of Alkoxyheteroarenes with Amines

et al. 2018

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“…88 Deuterium-labeling experiments support a reaction mechanism based on aromatic nucleophilic substitution (S N Ar). Other In(III) salts were less efficient catalytic systems.…”

Section: Nucleophilic Aromatic Substitution On Thiophenes Using Indolmentioning

confidence: 99%

Gallium and Indium Compounds in Homogeneous Catalysis

Dagorne

Fliedel

Frémont

2016

Encyclopedia of Inorganic and Bioinorganic Chemistry

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The present contribution highlights the most recent and representative developments on the use of Ga and In species in homogeneous catalysis. Recent studies of various ligand‐supported Ga(III) and In(III) compounds in cyclic esters polymerization catalysis for the production of biodegradable polyester materials are also included. Various organic transformations may now be catalyzed using Ga(III) and In(III) Lewis acids allowing access to a wide range of valuable organic molecules through diverse reaction sequences. The recent use of stable and robust N ‐heterocyclic carbene Ga(III) and In(III) compounds as strong π‐Lewis acid catalysts for various organic reactions is also discussed: such species are certainly promising for the future developments of Ga(III)‐ and In(III)‐mediated reactions. Although Lewis acid‐assisted reactions certainly dominate the field in Ga(III) and In(III) chemistry, discrete low‐valent In(I) species, presently emerging in catalysis, clearly display a distinct reactivity allowing their exploitation both as soft Lewis acids and alkyl‐/allyl‐/arylating agents.

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“…154 Iron-catalysed C−H bond activation has been used in the ortho arylation of arylpyridines by arylgrignard reagents. 154 Iron-catalysed C−H bond activation has been used in the ortho arylation of arylpyridines by arylgrignard reagents.…”

Section: Heterocyclic Systemsmentioning

confidence: 99%

Nucleophilic Aromatic Substitution

Crampton

2014

Organic Reaction Mechanisms Series

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Indium‐Catalyzed Heteroaryl–Heteroaryl Bond Formation through Nucleophilic Aromatic Substitution

Cited by 42 publications

References 56 publications

A Heteroarylamine Library: Indium‐Catalyzed Nucleophilic Aromatic Substitution of Alkoxyheteroarenes with Amines

A Heteroarylamine Library: Indium‐Catalyzed Nucleophilic Aromatic Substitution of Alkoxyheteroarenes with Amines

Gallium and Indium Compounds in Homogeneous Catalysis

Nucleophilic Aromatic Substitution

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