Atroposelective Synthesis of Tetrahydropyrrolo[3,2‐<i>c</i>]azepine Derivatives Through Gold(I)‐Catalyzed Hydroarylation

Gaillard, Quentin Gaignard; Han, Xu; Alix, Aurélien; Bour, Christophe; Guillot, Régis; Gandon, Vincent; Voituriez, Arnaud

doi:10.1002/adsc.202200828

Adv Synth Catal

2022

DOI: 10.1002/adsc.202200828

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Atroposelective Synthesis of Tetrahydropyrrolo[3,2‐c]azepine Derivatives Through Gold(I)‐Catalyzed Hydroarylation

Quentin Gaignard Gaillard

Xu Han

Aurélien Alix

et al.

Abstract: A series of enantioenriched substituted tetrahydropyrrolo[3,2‐c]azepine products possessing an axial chirality were synthesized in 63–99% yield through a gold(I)‐catalyzed hydroarylation. DFT calculations rationalized the reactivity observed for the formation of such complex molecular frameworks and guided our choice in the pyrrole N‐substituent to isolate configurationally stable compounds.

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Gold(I)-Catalyzed Substitution-Controlled Syntheses of Spiro[indoline-3,3′-pyrrolidine] and Spiro[indoline-3,3′-piperidine] Derivatives

Zhu

Zhang

et al. 2023

J. Org. Chem.

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and spiro[indoline-3,3′-piperidine] derivatives were synthesized in a substitutioncontrolled manner under the catalysis of cationic gold(I) species in the presence of Hantzsch ester (HEH). The optimal reaction condition was determined by screening, and the functional group tolerances of these two pathways were examined by readily synthetic substrates. The endo and exo selectivities of these cyclizations were elucidated by density functional theory calculations, and a plausible mechanism for these transformations was proposed.

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Gold(I)-Catalyzed Substitution-Controlled Syntheses of Spiro[indoline-3,3′-pyrrolidine] and Spiro[indoline-3,3′-piperidine] Derivatives

Zhu

Zhang

et al. 2023

J. Org. Chem.

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show abstract

Gold/HNTf₂-Cocatalyzed Asymmetric Annulation of Diazo-Alkynes: Divergent Construction of Atropisomeric Biaryls and Arylquinones

Wang,

Liu,

et al. 2024

J. Am. Chem. Soc.

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Due to the inherent challenges posed by the linear coordination of gold(I) complexes, asymmetric gold-catalyzed processes remain challenging, particularly in the atroposelective synthesis of axially chiral skeletons. Except for extremely few examples of intramolecular annulations, the construction of axial chirality via asymmetric goldcatalyzed intermolecular alkyne transformation is still undeveloped. Herein, a gold/HNTf 2 -cocatalyzed asymmetric diazo-alkyne annulation is developed, allowing the atroposelective and divergent synthesis of chiral non-C 2symmetric biaryls and arylquinones in generally good to excellent yield (up to 93% yield) and enantioselectivity (up to 99% ee), with broad substrate scope. Notably, this work represents the first gold-catalyzed atroposelective construction in an intermolecular manner. More interestingly, this strategy is successfully extended to the first asymmetric construction of sevenmembered-ring atropisomers bearing one carbon-centered chirality in excellent diastereoselectivity and high enantioselectivity (up to 93% ee and 50:1 dr). Remarkably, the utility of this methodology is further illustrated by the successful application of a representative axially chiral ligand in a series of enantioselective reactions. Importantly, the Brønsted acid as a proton-shuttle cocatalyst significantly promotes this asymmetric annulation. Additionally, the origin of enantioselectivity of this annulation and the role of HNTf 2 are disclosed by density functional calculations and control experiments.

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Atroposelective Synthesis of Tetrahydropyrrolo[3,2‐c]azepine Derivatives Through Gold(I)‐Catalyzed Hydroarylation

Cited by 2 publications

References 62 publications

Gold(I)-Catalyzed Substitution-Controlled Syntheses of Spiro[indoline-3,3′-pyrrolidine] and Spiro[indoline-3,3′-piperidine] Derivatives

Gold(I)-Catalyzed Substitution-Controlled Syntheses of Spiro[indoline-3,3′-pyrrolidine] and Spiro[indoline-3,3′-piperidine] Derivatives

Gold/HNTf₂-Cocatalyzed Asymmetric Annulation of Diazo-Alkynes: Divergent Construction of Atropisomeric Biaryls and Arylquinones

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Product

Resources

About

Atroposelective Synthesis of Tetrahydropyrrolo[3,2‐c]azepine Derivatives Through Gold(I)‐Catalyzed Hydroarylation

Cited by 2 publications

References 62 publications

Gold(I)-Catalyzed Substitution-Controlled Syntheses of Spiro[indoline-3,3′-pyrrolidine] and Spiro[indoline-3,3′-piperidine] Derivatives

Gold(I)-Catalyzed Substitution-Controlled Syntheses of Spiro[indoline-3,3′-pyrrolidine] and Spiro[indoline-3,3′-piperidine] Derivatives

Gold/HNTf2-Cocatalyzed Asymmetric Annulation of Diazo-Alkynes: Divergent Construction of Atropisomeric Biaryls and Arylquinones

Contact Info

Product

Resources

About

Gold/HNTf₂-Cocatalyzed Asymmetric Annulation of Diazo-Alkynes: Divergent Construction of Atropisomeric Biaryls and Arylquinones