Pd-Catalyzed Asymmetric Dearomative Arylation of Indoles via a Desymmetrization Strategy

Nie, Yu-Han; Komatsuda, Masaaki; Yang, Ping; Zheng, Chao; Yamaguchi, Junichiro; You, Shu‐Li

doi:10.1021/acs.orglett.2c00129

Cited by 16 publications

(7 citation statements)

References 59 publications

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“…Early development of an enantioselective version were however tedious. 24 More recently, a similar intramolecular asymmetric arylation on indole C3 position has been described by desymmetrization of compounds 21, 25 that can be efficiently transformed into spiroindolenines 22 with excellent ees in the presence of phosphoramidite L3a*, with a total diastereoselectivity in most cases (Scheme 7.B). The authors observed an important influence of the electronic properties of the aromatic ring substituents.…”

Section: Coupling Reactions With Halide Partnersmentioning

confidence: 94%

Spiroindoles as Intermediates/Products in Transition Metal Catalyzed Dearomatization of Indoles

Buttard

Guinchard

2023

Preprint

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Spirocyclic indole derivatives are fascinating tridimensional molecular scaffolds, from both a synthetic and biological point of view. Among the diversity of strategies developed to access this kind of structures, transition metal catalysis recently led to impressive advances, especially in order to tame the unique reactivity of the dearomatized spirocyclic intermediates. These species can indeed evolve towards both spirocyclic or non-spirocyclic products through rearomatization-driven processes which are at the same time highly challenging to control but also source of a large structural diversity. This review highlights the most prominent methods of the last decade allowing to trigger a spirocyclization on indole derivatives tethered with a transition metal-activable functional group, leading to both spirocyclic and rearomatized products. The discussion is particularly focused on the reactivity and the complex mechanistic features regarding the evolution of the spiroindoleninium intermediate, highly dependent on the catalytic system.

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Section: Coupling Reactions With Halide Partnersmentioning

confidence: 94%

Spiroindoles as Intermediates/Products in Transition Metal Catalyzed Dearomatization of Indoles

Buttard

Guinchard

2023

Preprint

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“…Early developments of an enantioselective version were, however, tedious . More recently, a similar intramolecular asymmetric arylation on the indole C3 position has been described by desymmetrization of compounds 21 , which can be efficiently transformed into spiroindolenines 22 with excellent enantio- and diastereoselectivity in the presence of the phosphoramidite ligand L3a* (Scheme .B). The authors observed an important influence of the electronic properties of the aromatic ring substituents.…”

Section: Palladium Catalysismentioning

confidence: 99%

Spiroindoles as Intermediates/Products in Transition Metal-Catalyzed Dearomatization of Indoles

Buttard

Guinchard

2023

ACS Catal.

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Spirocyclic indole derivatives are fascinating tridimensional molecular scaffolds from both a synthetic and a biological point of view. Among the many strategies developed to access these structures, transition metal catalysis has recently led to impressive advances, especially relying on the unique reactivity of the dearomatized spirocyclic intermediates. These species can indeed evolve toward both spirocyclic or nonspirocyclic products through rearomatization-driven processes, which are at the same time highly challenging to control but also a source of large structural diversity. This review highlights the most prominent methods of the past decade that involve a spirocyclization on indole derivatives tethered to a functional group that may be activated by a transition metal, leading to both spirocyclic and rearomatized products. The discussion is particularly focused on the reactivity of the spiroindoleninium intermediate and the complex mechanistic features regarding its evolution, which are highly dependent on the catalytic systems.

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“…Furthermore, step and atom economical stereoselective construction of such molecules from simple feedstocks is undoubtedly of significant importance in modern research. Desymmetrization of prochiral bis-indoles is one straightforward strategy to build bis(indolyl) alkaloid type architectures. − Xu and Shi et al reported a gold-catalyzed asymmetric desymmetrization of bis(indolyl)-5-alkynes to give bis(indole) tetrahydropyridines (Scheme -Ia) . Catalytic asymmetric dearomatization (CADA) of bis-indoles was also reported to afford diverse indole/indoline containing heterocycles using transition-metal (Ir, Pd, and Pt; Schemes -Ib) and thiourea catalysts (Scheme -Ic).…”

mentioning

confidence: 99%

“…Desymmetrization of prochiral bis-indoles is one straightforward strategy to build bis(indolyl) alkaloid type architectures. − Xu and Shi et al reported a gold-catalyzed asymmetric desymmetrization of bis(indolyl)-5-alkynes to give bis(indole) tetrahydropyridines (Scheme -Ia) . Catalytic asymmetric dearomatization (CADA) of bis-indoles was also reported to afford diverse indole/indoline containing heterocycles using transition-metal (Ir, Pd, and Pt; Schemes -Ib) and thiourea catalysts (Scheme -Ic). Recently, Li et al reported an I 2 -catalyzed desymmetrization strategy via cyclo-isomerization of ynamides to various bis(indolyl) tetrahydropyridines and pyrroles (Schemes -Id) .…”

mentioning

confidence: 99%

Catalyst-Controlled Diastereoselective Synthesis of Bridged [3.3.1] Bis(Indolyl)-Oxanes and Oxepanes via Desymmetrization of Bis(Indolyl)-Cyclohexadienones

et al. 2023

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A catalyst-controlled divergent synthesis of bridged [3.3.1] bis(indolyl)-oxanes and cis-[6.7] fused bis(indolyl) oxepanes via diastereoselective desymmetrization of bis(indolyl)-cyclohexadienones is presented for the first time. The reaction is highly atom-and step-economic, furnishing sp 3 -rich functionalized bis(indolyl) derivatives in good to excellent yields with wide substrate scope. The reaction proceeds through Friedel−Crafts alkylation followed by catalyst-controlled selective C−C bond formation/rearrangement. Gram scale synthesis and synthetic utility to generate bis(indolyl) alkaloid-like molecular diversity were also illustrated.

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Pd-Catalyzed Asymmetric Dearomative Arylation of Indoles via a Desymmetrization Strategy

Cited by 16 publications

References 59 publications

Spiroindoles as Intermediates/Products in Transition Metal Catalyzed Dearomatization of Indoles

Spiroindoles as Intermediates/Products in Transition Metal Catalyzed Dearomatization of Indoles

Spiroindoles as Intermediates/Products in Transition Metal-Catalyzed Dearomatization of Indoles

Catalyst-Controlled Diastereoselective Synthesis of Bridged [3.3.1] Bis(Indolyl)-Oxanes and Oxepanes via Desymmetrization of Bis(Indolyl)-Cyclohexadienones

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