Cationic Gallium(III) Halide Complexes: A New Generation of π‐Lewis Acids

Tang, S. C.; Monot, Julien; El‐Hellani, Ahmad; Michelet, Bastien; Guillot, Régis; Bour, Christophe; Gandon, Vincent

doi:10.1002/chem.201201202

Cited by 76 publications

(46 citation statements)

References 65 publications

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“…We also investigated the cycloisomerization of an enyne and trapping with anisole under gallium catalysis (Scheme 12). 40 A better yield was obtained in this case when using the gallium/silver procedure instead of the preformed cationic species. The product 43 was obtained as a separable regioisomeric mixture with respect to the position of the C=C double bond.…”

Section: Scheme 9 Indium-catalyzed Polycyclization Of Compound 35mentioning

confidence: 92%

New Procedures for Catalytic Carbophilic Activation by Gold and Gallium π-Acids

Bour

Gandon

2015

Synlett

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Dedicated, with admiration, to K. Peter C. Vollhardt NuH Nu H Nu H or R 3 PAuCl/LA LA = Cu(OTf) 2 , In(OTf) 3 , Bi(OTf) 3 , etc. or (NHC)GaCl 2 + NuH = arene, alkene, β-keto amide, -OH, -NH, etc.Abstract Cationic gold(I) complexes are soft Lewis acids that are able to trigger numerous types of nucleophilic attack onto alkenes, allenes, and alkynes (π-acid catalysis). In this account, we initially summarize the novel methods that we have developed to generate such catalysts by silver-free activation of ligated gold(I) chlorides. The advantages of this approach are the use of lower quantities of gold and the ability to scale-up transformations during which the standard gold/silver catalytic system is rapidly decomposed. In the second part, the synthesis and catalytic activity of original organogallium compounds is described. We have shown that (NHC)GaCl 2 +

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Section: Scheme 9 Indium-catalyzed Polycyclization Of Compound 35mentioning

confidence: 92%

New Procedures for Catalytic Carbophilic Activation by Gold and Gallium π-Acids

Bour

Gandon

2015

Synlett

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“…The salt [(IDipp)GaCl 2 ][SbF 6 ] (IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) displayed the highest activity (30). 42, 43 However, the latter is moisture sensitive and in situ generation of the active cationic species is preferred. At best, a 1:2 [(IDipp)GaCl 3 ]/AgSbF 6 catalytic mixture (1 mol% in Ga) led to the quantitative formation of the desired product.…”

Section: N-heterocyclic Carbene (Nhc) Ligandsmentioning

confidence: 99%

“…The InCl 3 -catalyzed dehydrative addition of thiols to allenols was reported to produce stereoselectively (E,E)-1,3-dien-2-yl-sulfanes (43). 71 Depending on thiol acidity, two reaction mechanisms were proposed, involving a thiol nucleophilic attack at either a π-allenylindium complex or an In(III) alkoxide intermediate.…”

Section: Dehydrative Thiolation Of Allenols: Synthesis Of 13-dien-2-mentioning

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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“…A possible solution for those cases is hydrogen transfer catalysis, in which hydrogen is transferred from a molecule such as isopropanol or 1,4‐cyclohexadiene to the substrate under mild conditions and usually promoted by transition metal catalysts . A few years ago, the synthesis of [(IDipp)GaCl 2 ][SbF 6 ] [IDipp=1, 3‐bis{2, 6‐bis(diphenylmethyl)‐4‐methylphenyl}‐1,3‐dihydro‐imidazol‐2‐ylidene, 3 , Scheme ] was reported, a compound that exists as a tight ion pair in the solid state and likely in non‐ to moderately polar solvents, but in which the Ga⋅⋅⋅F⋅⋅⋅Sb bridge can be split by donors such as nitriles and also π‐systems such as olefins and alkynes. Despite the high reactivity of species 3 , its synthesis and handling is rather simple given that it can be generated and used in situ from the air‐stable adduct (IDipp)GaCl 3 and commercially available Ag[SbF 6 ].…”

Section: Introductionmentioning

confidence: 99%

“…Both Ga species 3 and 4 also catalyze the intramolecular hydroarylation of alkynes, and the resulting styrene derivative can either undergo a second hydroarylation step or be reduced via transfer hydrogenation as discussed above (Scheme ). The two catalysts are tolerant of ether, ester and nitro functional groups, and the use of Ga I catalyst 4 decreases unwanted polymerization side reactions …”

Section: Introductionmentioning

confidence: 99%

Recent Developments on the Use of Group 13 Metal Complexes in Catalysis

Dagorne

Wehmschulte

2018

ChemCatChem

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The present Minireview highlights the most representative and emerging developments reported since 2012 on the use of well‐defined group 13 metal species in homogeneous catalysis. Apart from their use in polymerization catalysis, group 13 metal catalysts have primarily been developed for the functionalization of polar/unsaturated small molecules, with most reactions involving C−C, C−O or C−N double or triple bond functionalization (most frequently (C6F5)3Al and low‐coordinate Al cations). The exploitation of group 13 catalysts for CO2 functionalization chemistry has made remarkable advances over the past five years, including the development of Al‐ and Ga‐based complexes for CO2 hydrosilylation/hydroboration. Highly effective Al catalysts for the production of cyclic carbonates via CO2/epoxide coupling are also discussed. The emerging use of simple Group 13 metal Lewis pairs for the controlled polymerization of polar monomers is also reviewed.

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Cationic Gallium(III) Halide Complexes: A New Generation of π‐Lewis Acids

Cited by 76 publications

References 65 publications

New Procedures for Catalytic Carbophilic Activation by Gold and Gallium π-Acids

New Procedures for Catalytic Carbophilic Activation by Gold and Gallium π-Acids

Gallium and Indium Compounds in Homogeneous Catalysis

Recent Developments on the Use of Group 13 Metal Complexes in Catalysis

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