Group 13 Metal‐Mediated Organic Reactions

Dagorne, Samuel; Bellemin‐Laponnaz, Stéphane

doi:10.1002/9780470976548.ch11

Cited by 10 publications

(8 citation statements)

References 337 publications

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“…Then, InCl 3 was evaluated. InCl 3 appeared to be attractive for two reasons: (i) it is unaffected by air or water and can be easily handled without any apparent toxicity; and (ii) it exhibits a low heterophilicity, and therefore, nitrogen- and oxygen-containing functional groups are tolerated in the presence of indium compounds . We were pleased to see that, using InCl 3 , the yield of capronitrile 2 of more than 97% was obtained in 7 h at 200 °C (Figure ).…”

Section: Resultsmentioning

confidence: 96%

“…It also appears that the cost is a crucial parameter that limits the development of other group 13 metal-mediated organic transformations. However, with the exception of thallium which is highly toxic, the unique properties of gallium and indium in organic transformations make them interesting catalysts for the transnitrilation reaction . However, yields were comparable using AlCl 3 or GaCl 3 as a catalyst in reagent-grade acetonitrile.…”

Section: Resultsmentioning

confidence: 99%

“…However, with the exception of thallium which is highly toxic, the unique properties of gallium and indium in organic transformations make them interesting catalysts for the transnitrilation reaction. 34 However, yields were comparable using AlCl 3 or GaCl 3 as a catalyst in reagentgrade acetonitrile. Again, the water sensitivity of GaCl 3 could explain the rather low efficiency of the catalyst.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Therefore, efficient catalytic procedures for the transnitrilation of carboxylic acid are still in great demand. Herein we report that the nitrile synthesis via the acid–nitrile exchange reaction may be accomplished in a classical batch reactor, and in a high yield using a catalytic quantity of a readily available, water-tolerant, innocuous Lewis acid, that is, indium trichloride (InCl 3 ). , Finally, the theoretical mechanism is revisited (experimentally and computationally) and a kinetic model capturing the experimental trends is proposed and optimized.…”

Section: Introductionmentioning

confidence: 99%

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Direct Synthesis of Nitriles from Carboxylic Acids Using Indium-Catalyzed Transnitrilation: Mechanistic and Kinetic Study

et al. 2019

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Aliphatic and aromatic carboxylic acids can be quantitatively converted to the corresponding nitriles in the presence of catalysts using acetonitrile both as a solvent and reactant at 200 °C. This transformation is based on the acid–nitrile exchange (i.e., transnitrilation) and uses a nontoxic and water resistant catalyst, indium trichloride (InCl3). The mechanism of the transnitrilation was investigated both experimentally and computationally and compared to the previously proposed mechanism. In contrast to the usually assumed formation of amide as an intermediate, transnitrilation is an equilibrium reaction and proceeds via an equilibrated Mumm reaction with the formation of an imide as an intermediate. A simple and reversible mechanism was proposed for this reaction, which was validated by kinetics measurement and by density functional theory calculations of the reaction intermediates and reaction mechanisms.

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Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Direct Synthesis of Nitriles from Carboxylic Acids Using Indium-Catalyzed Transnitrilation: Mechanistic and Kinetic Study

et al. 2019

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“…Well-defined group 13 organo compounds supported by various N- and/or O-based multidentate chelating ligands, such as, for instance, salen- and salan-derived ligands, have been widely studied and have found numerous applications in homogeneous catalysis ranging from their use in the mediation of various Lewis acid assisted organic reactions to that in polymerization catalysis of polar monomers (cyclic esters, epoxides). − Efficient discrete group 13 based catalysts developed thus far mainly consist of five-coordinate or higher species of the type (L 2 X 2 )MX′ or (L 2 X 2 )M(X′)(L′) . Indeed, in such complexes, the high coordination of the metal center and the formation of robust (L 2 X 2 )M chelates typically ensure an excellent stability and disfavor the formation of undesirable aggregates.…”

Section: Introductionmentioning

confidence: 99%

A Discrete N,O,N-Supported Gallium Amido Complex for the Intermolecular Hydroamination of Terminal Alkynes

Hild

Dagorne

2012

Organometallics

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The diamino-ether ligand {(C 5 H 9 )NH-C 6 H 4 } 2 O (1) was found to readily react with 0.5 equiv of Ga 2 (NMe 2 ) 6 via an amine elimination route to afford the N,O,N-supported Ga amido species {η 3 -N,O,N-((C 5 H 9 )N-C 6 H 4 ) 2 O}GaNMe 2 (2) in a reasonable yield (51%). As determined by X-ray crystallography, the four-coordinate Ga center in 2 adopts an unusual trigonalmonopyramidal geometry. Compound 2 effectively catalyzes the hydroamination of terminal alkynes (such as 1-hexyne and phenylacetylene) in the presence of primary amines (aniline and butylamine). Kinetic studies on the latter catalytic reactions suggest that these proceed with a first-order rate dependence on alkyne and on species 2. In preliminary studies aiming at the isolation of intermediates relevant to the present catalysis, the dimeric Ga complex [{η 2 -N,N-((C 5 H 9 )N-C 6 H 4 ) 2 O}Ga(μ-NHPh)] 2 (3) was synthesized by an aminolysis reaction between compound 2 and aniline; its identity was confirmed by X-ray crystallographic analysis.

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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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Group 13 Metal‐Mediated Organic Reactions

Cited by 10 publications

References 337 publications

Direct Synthesis of Nitriles from Carboxylic Acids Using Indium-Catalyzed Transnitrilation: Mechanistic and Kinetic Study

Direct Synthesis of Nitriles from Carboxylic Acids Using Indium-Catalyzed Transnitrilation: Mechanistic and Kinetic Study

A Discrete N,O,N-Supported Gallium Amido Complex for the Intermolecular Hydroamination of Terminal Alkynes

Gallium and Indium Compounds in Homogeneous Catalysis

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