π-Extension of heterocycles <i>via</i> a Pd-catalyzed heterocyclic aryne annulation: π-extended donors for TADF emitters

Spence, Katie A.; Chari, Jason V.; Niro, Mattia Di; Susick, Robert B.; Ukwitegetse, Narcisse; Djurovich, Peter I.; Thompson, Mark E.; Garg, Neil K.

doi:10.1039/d2sc01788a

Cited by 14 publications

(11 citation statements)

References 56 publications

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“…This has allowed access to many value-added species such as ligands, natural products, and other conjugated compounds. [3][4][5][6][7][8][9][10][11] Although arynes have been used with much success, aryne methodology continues to be plagued with regioselectivity challenges. 8,[12][13][14][15] Reactions of unsymmetrical arynes can (and often will) result in mixtures of regioisomeric products and lead to poor reaction efficiency.…”

Section: Arynes As Building Blocksmentioning

confidence: 99%

Insights into the Regioselectivity of Metal-Catalyzed Aryne Reactions

Plasek,

Denman,

Roberts

2023

Synlett

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The synthetic potential of unsymmetrically substituted aryne intermediates is significantly hindered by regioselectivity issues. Current methods for inducing regioselectivity all rely on substrate control and are focused on non-metallated arynes. Before our initial disclosure, there was no systematic study regarding the regioselectivity of metal-catalyzed aryne reactions. By exploiting ligand control, we have induced regioselectivity in a palladium-catalyzed aryne annulation to form phenanthridinones (up to 9:91 r.r.). Through this study we have investigated: ligand effects, influence of steric perturbation, and the impact of the aryne precursor.1 Introduction2 Inducing Regioselectivity via Ligand Control3 A Comparison of o-Borylaryl Triflate Aryne Precursors to Kobayashi Aryne Precursors4 Conclusion

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Section: Arynes As Building Blocksmentioning

confidence: 99%

Insights into the Regioselectivity of Metal-Catalyzed Aryne Reactions

Plasek,

Denman,

Roberts

2023

Synlett

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“…Cyclization requires good LUMO-HUMO orbital matching, and the benzene intermediate has a low LUMO, which is easy for various dienophiles to undergo [4 + 2], [2 + 2] cycloaddition, and [3 + 2] dipolar cycloaddition. 30,31 In the past decade, various benzyl precursor cyclization methods have been developed to synthesize nitrogencontaining heterocyclic compounds with potential applications providing a new route.…”

Section: Introductionmentioning

confidence: 99%

Advances in the synthesis of nitrogen-containing heterocyclic compounds byin situbenzyne cycloaddition

Huang

2023

RSC Adv.

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“…Arynes are highly reactive intermediates which have enabled the synthesis of natural products, ligands, and conjugated materials. − A substantial challenge is posed when using unsymmetrically substituted arynes as they can produce multiple regioisomeric products. ,− This severely limits the potential of aryne intermediates toward synthetic applications . A number of elegant experimental and computational models have been developed to probe the origins of selectivity for aryne reactions in the absence of metals. − In all of these examples regioselectivity is substrate controlled.…”

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confidence: 99%

Ligand-Induced Regioselectivity in Metal-Catalyzed Aryne Reactions Using Borylaryl Triflates as Aryne Precursors

2023

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The utility of reactions using unsymmetrically substituted aryne intermediates can be negatively impacted by issues with regioselectivity as these reactions are substrate controlled. This leaves no avenues for improving regioselectivity without altering the substrate which has led to numerous reports about how to enhance or reverse this regioselectivity in metal-free aryne reactions by changing the electronics. No such studies exist for systems with metal-bound aryne intermediates, which often suffer from worse regioselectivities. Herein we report a means of achieving regioselectivity in a metal-catalyzed aryne difunctionalization via catalyst control. Through the use of an unsymmetrical ligand environment, selectivity can be induced (up to 9:91 r.r.). These investigations demonstrate that catalyst design can influence selectivity in metal-catalyzed aryne reactions.

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π-Extension of heterocycles via a Pd-catalyzed heterocyclic aryne annulation: π-extended donors for TADF emitters

Abstract: We report the annulation of heterocyclic building blocks to access pi-extended polycyclic aromatic hydrocarbons (PAHs). The method involves the trapping of short-lived hetarynes with catalytically-generated biaryl palladium intermediates and allows...

Cited by 14 publications

References 56 publications

Insights into the Regioselectivity of Metal-Catalyzed Aryne Reactions

Insights into the Regioselectivity of Metal-Catalyzed Aryne Reactions

Advances in the synthesis of nitrogen-containing heterocyclic compounds byin situbenzyne cycloaddition

Ligand-Induced Regioselectivity in Metal-Catalyzed Aryne Reactions Using Borylaryl Triflates as Aryne Precursors

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