Asymmetric Intramolecular Hydroamination of Allenes using Mononuclear Gold Catalysts

Michon, Christophe; Medina, Florian; Abadie, Marc‐Antoine; Agbossou‐Niedercorn, Francine

doi:10.1021/om4009058

Cited by 52 publications

(23 citation statements)

References 185 publications

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“…Along our studies on gold‐catalysed hydroamination reactions, we noticed a positive silver effect for binuclear gold(I) catalysts but none for mononuclear ones –. Indeed, a phosphoramidite mononuclear gold(I) cationic species led to an unchanged reaction outcome while removing AgCl by filtration through Celite or a PTFE filter prior to the catalysis.…”

Section: Introductionmentioning

confidence: 86%

Gold(I)‐Catalysed Asymmetric Hydroamination of Alkenes: A Silver‐ and Solvent‐Dependent Enantiodivergent Reaction

Abadie

Trivelli

Medina

et al. 2017

Chemistry A European J

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In the present study, we report the first silver-dependent enantiodivergent gold-catalysed reaction. The asymmetric intramolecular hydroamination of alkenes catalysed by the combination of a single chiral binuclear gold(I) chloride complex and silver perchlorate can afford both enantiomers of the products by a simple solvent change from toluene to methanol. Such an enantiodivergent reaction is strictly independent of the reaction temperature or of the nature of the catalyst anion and displays the same first-order kinetic rate law with respect to substrate concentration in both solvents. Beyond a simple solvent effect the enantioinversion is controlled by gold-silver chloride adducts which occur only in methanol and allow a dual activation of the reagent. While one single gold atom activates the alkene moiety, the other gold atom forms an oxophilic gold-silver chloride adduct which is likely to interact with the carbamate function. By comparison with toluene, which affords (S)-enantiomer, this proximal and bimetallic activation would allow an opposite stereodifferentiation of the two diastereomeric intermediates during the final protodeauration step and lead therefore to the (R)-enantiomer.

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Section: Introductionmentioning

confidence: 86%

Gold(I)‐Catalysed Asymmetric Hydroamination of Alkenes: A Silver‐ and Solvent‐Dependent Enantiodivergent Reaction

Abadie

Trivelli

Medina

et al. 2017

Chemistry A European J

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“…Only two articles devoted to this subject have appeared, reported independently by Shi [82] and Agbossou-Niedercorn [115,118] (Scheme 32). Unfortunately, higher temperature was needed to reach moderate yield, which was responsible for low enantioselectivity.…”

Section: Furan Pyrrolidine and Indanone Derivativesmentioning

confidence: 99%

“…In contrast to gold(I) complexes, the synthetic efforts leading to their gold(III) counterparts have met with little success to date and there have only been two reports devoted to chiral gold(III) complexes. The seminal work of Michon and Agbossou-Niedercorn [115,118] proved that chiral Scheme 45. Intermolecular asymmetric hydroazidation and hydroamination of allenes.…”

Section: The Synthesis Of Gold(iii) Complexesmentioning

confidence: 99%

Chiral N-heterocyclic Carbene Gold Complexes: Synthesis and Applications in Catalysis

Michalak

Kośnik

2019

Catalysts

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N-Heterocyclic carbenes have found many applications in modern metal catalysis, due to the formation of stable metal complexes, and organocatalysis. Among a myriad of N-heterocyclic carbene metal complexes, gold complexes have gained a lot of attention due to their unique propensity for the activation of carbon-carbon multiple bonds, allowing many useful transformations of alkynes, allenes, and alkenes, inaccessible by other metal complexes. The present review summarizes synthetic efforts towards the preparation of chiral N-heterocyclic gold(I) complexes exhibiting C 2 and C 1 symmetry, as well as their applications in enantioselective catalysis. Finally, the emerging area of rare gold(III) complexes and their preliminary usage in asymmetric catalysis is also presented. Scheme 3. The synthesis of a gold(I) complex from (R)-1-aminotetralin.An elegant approach to C2-symmetric gold(I) complexes was described by Czekelius et al. [72] (Scheme 4), inspired by previous Herrmann's work [73]. The synthetic approach involves chiral amines 24, readily available from the corresponding phenylacetic acid 22 via the Friedel-Crafts reaction of bromobenzene and fractional crystallization of the corresponding tartaric acid amine salt upon reductive amination. The resulting amine 24 was further formylated and subjected to Bischler-Napieralski cyclization to give 3-aryl-substituted dihydroisoquinoline 25. Subsequent reductive coupling afforded the basic diamine skeleton 26 into a single diastereomer, which appeared a perfect platform for structural ligand diversification via Suzuki coupling. The functionalized diamines 26 were then cyclized into imidazolium salts 27 with triethyl orthoformate to give the products with yields in the range of 49-94% (for selected examples, see Scheme 4). The formation of gold(I) complexes 28 was accomplished under rather unusual conditions, by the reaction of gold(I) chloride with a carbene generated by the action of KOtBu. Scheme 4. The synthesis of C2-symmetric gold(I) complexes accessible via a reductive coupling. The application of other chiral building blocks has recently been reported by the Toste group (Scheme 5) [74]. Besides chiral amines, amino alcohols 29 were also utilized in the synthesis of C2-Scheme 3. The synthesis of a gold(I) complex from (R)-1-aminotetralin.An elegant approach to C 2 -symmetric gold(I) complexes was described by Czekelius et al. [72] (Scheme 4), inspired by previous Herrmann's work [73]. The synthetic approach involves chiral amines 24, readily available from the corresponding phenylacetic acid 22 via the Friedel-Crafts reaction of bromobenzene and fractional crystallization of the corresponding tartaric acid amine salt upon reductive amination. The resulting amine 24 was further formylated and subjected to Bischler-Napieralski cyclization to give 3-aryl-substituted dihydroisoquinoline 25. Subsequent reductive coupling afforded the basic diamine skeleton 26 into a single diastereomer, which appeared a perfect platform for structural ligand diversification via Suzuki...

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“…In addition to the modularity provided by a convergent catalyst synthesis, this system was attractive as only one gold atom is required to accomplish previously published transformations with similar levels of conversion and enantioselectivity. Michon et al have also shown BINOL-based phosphoramidite catalysts are relatively competent at forming enantioenriched pyrrolidines [70]. In addition to these conventional approaches to hydrofunctionalization of allenes, Lipshutz et al have demonstrated the ability to synthesize enantioenriched lactones inside a PEGylated micelle using water as the bulk solution [71].…”

Section: Intramolecular Cyclizationsmentioning

confidence: 99%

Enantioselective Gold-Catalyzed Synthesis of Heterocyclic Compounds

Miles

Toste

2015

Topics in Heterocyclic Chemistry

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Asymmetric gold-catalyzed syntheses of a diverse range of heterocycles are described herein. This chapter outlines efforts toward the construction of these molecules via intermolecular, intramolecular, and tandem cyclization strategies. Additionally, asymmetric hydrogenation and epoxidation approaches are detailed. These methodologies generally utilize substrates containing soft, unsaturated carbon-carbon bonds, which can easily interact with the carbophilic gold atom(s). Mostly through the use of bis-or monophosphine ligands, modest to excellent yields and enantioselectivities are obtained for a variety of partially and fully saturated heterocycles. Although steric variation of the phosphine catalyst is the most commonly used strategy for enantioinduction, the use of chiral counteranions has proven useful for more challenging transformations. This chapter includes only examples of syntheses where a chiral gold catalyst is used in the direct formation of the heterocycle; examples of pendant functionalization of an existing heterocycle or chirality transfer from enantioenriched substrate to product are not included.

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Asymmetric Intramolecular Hydroamination of Allenes using Mononuclear Gold Catalysts

Cited by 52 publications

References 185 publications

Gold(I)‐Catalysed Asymmetric Hydroamination of Alkenes: A Silver‐ and Solvent‐Dependent Enantiodivergent Reaction

Gold(I)‐Catalysed Asymmetric Hydroamination of Alkenes: A Silver‐ and Solvent‐Dependent Enantiodivergent Reaction

Chiral N-heterocyclic Carbene Gold Complexes: Synthesis and Applications in Catalysis

Enantioselective Gold-Catalyzed Synthesis of Heterocyclic Compounds

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