Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Chemical Reviews, Год журнала: 2023, Номер 123(16), С. 10079 - 10134

Опубликована: Авг. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Язык: Английский

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Catalytic asymmetric (3 + 3) cycloaddition between different 2-indolylmethanols

Science China Chemistry, Год журнала: 2024, Номер 67(8), С. 2629 - 2636

Опубликована: Июнь 26, 2024

Язык: Английский

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Pd-Catalyzed Asymmetric Larock Indole Synthesis to Access Axially Chiral N-Arylindoles

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5493 - 5501

Опубликована: Фев. 13, 2024

Larock indole synthesis is one of the most straightforward and efficient methods for indoles; however, there has been no asymmetric version yet construction indole-based axially chiral N-arylindoles since its initial report in 1991. Herein we first example an by employing a sulfinamide phosphine (SadPhos) ligand (Ming-Phos) with palladium. It allows rapid wide range N-arylindole compounds good yields up to 98:2 er. The application this unique scaffold as organocatalyst promising. Furthermore, kinetic study revealed that alkyne migratory insertion rate-determining step, which proven density functional theory (DFT) calculations. Additionally, DFT studies also suggest N–C dihedral difference caused steric hindrance contributes enantioselectivity control.

Язык: Английский

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Chiral Acid-Catalyzed Atroposelective Indolization Enables Access to 1,1′-Indole-Pyrroles and Bisindoles Bearing a Chiral N–N Axis

Organic Letters, Год журнала: 2023, Номер 25(9), С. 1553 - 1557

Опубликована: Март 1, 2023

We present herein a highly atroposelective indolization for the efficient synthesis of 1,1'-biheteroaryls bearing chiral N-N axis. Under cooperative catalysis phosphoric acid and InBr3, reactions between 2,3-diketoesters 1,3-dione-derived enamines resulted in enantioselective construction 1,1'-pyrrole-indoles with up to 92% yield, 94% enantiomeric excess (ee), or bisindoles ee. Derivatizations these compounds diverse functionalized linked axially biheteroaryls have also been demonstrated.

Язык: Английский

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Pd-catalyzed asymmetric Larock reaction for the atroposelective synthesis of N─N chiral indoles

Science Advances, Год журнала: 2024, Номер 10(19)

Опубликована: Май 10, 2024

Atropisomeric indoles defined by a N─N axis are an important class of heterocycles in synthetic and medicinal chemistry material sciences. However, they remain heavily underexplored due to limited methods challenging stereocontrol over the short bonds. Here, we report highly atroposelective access axially chiral via asymmetric Larock reaction. This protocol leveraged powerful role phosphoramidite ligand attenuate common dissociation original reaction, forming with excellent functional group tolerance high enantioselectivity palladium-catalyzed intermolecular annulation between readily available o -iodoaniline alkynes. The multifunctionality prepared allowed diverse post-coupling transformations, affording broad array functionalized indoles. Experimental computational studies have been conducted explore reaction mechanism, elucidating enantio-determining rate-limiting steps.

Язык: Английский

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Rhodium(III)-Catalyzed Atroposelective Indolization to Access Planar-Chiral Macrocycles

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(42), С. 29214 - 29223

Опубликована: Окт. 9, 2024

Macrocycles incorporating conformationally defined indoles are widely found in bioactive natural products. However, the catalytic enantioselective synthesis of planar-chiral via indolization involving macrocyclization remains elusive. Herein, we present first rhodium(III)-catalyzed atroposelective macrocyclization, which involves C-H activation aniline, and a subsequent oxidation [3 + 2] annulation reaction with an intramolecular alkyne. This protocol achieves construction indoles, planar chirality control single step. Importantly, this strategy produces macrocyclic atropisomers bearing full-carbon ansa chains, represent challenging targets organic synthesis. Thermodynamic experiments revealed that rotational barrier chain-linked atropisomer was lower than oxa-ansa chain. The mechanism elucidated by computational studies, alkyne insertion steps collectively determined enantioselectivity.

Язык: Английский

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Silver-Catalyzed Direct Nucleophilic Cyclization: Enantioselective De Novo Synthesis of C–C Axially Chiral 2-Arylindoles

Organic Letters, Год журнала: 2023, Номер 25(3), С. 522 - 527

Опубликована: Янв. 18, 2023

Atropisomeric indoles widely exist in natural products, pharmaceuticals, functional materials, and catalysts for their featured biological activities, photoelectric properties, catalytic while facile de novo construction of this motif remains underexplored. Herein, we report a chiral silver phosphate-catalyzed direct 5-endo-dig nucleophilic cyclization 2-alkynylanilins under mild conditions, affording various C-C axially 2-arylindoles high to excellent yields enantioselectivities. Control experiments implied the cooperative catalysis AgOAc phosphoric acid, wherein former accelerated desired transformation latter improved enantioselectivity. In addition, as first example silver-catalyzed enantioselective synthesis indole skeletons, synthetic applications products' thermal stability have been investigated.

Язык: Английский

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Pd-Catalyzed Asymmetric Amination of Enamines: Expedient Synthesis of Structurally Diverse N–C Atropisomers

ACS Catalysis, Год журнала: 2023, Номер 13(11), С. 7680 - 7690

Опубликована: Май 23, 2023

The transition-metal-catalyzed cross-coupling of enamines is an attractive method for producing compounds with N–C chiral axis; however, it faces considerable challenges that remain unresolved. Herein, a palladium-catalyzed amination was developed to construct structurally diverse five–six biaryl and six–six nonbiaryl atropisomers. reaction mechanism explained using density functional theory calculations, which showed the involved Curtin–Hammett control. rotation occurred along coordinate until enantio-determining three-centered reductive elimination transition structure established stereochemistry. highly because its broad substrate scope, high stereoselectivity, simple catalytic system, good group tolerance, dynamic kinetic resolution.

Язык: Английский

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Asymmetric aza‐Friedel–Crafts Reaction of Cyclic Ketimines with 5‐Aminopyrazole Derivatives: Expedient Access to Pyrazole‐Based C2‐quaternary Indolin‐3‐Ones

Chemistry - A European Journal, Год журнала: 2023, Номер 29(20)

Опубликована: Янв. 5, 2023

A chiral phosphoric acid-catalyzed enantioselective aza-Friedel-Crafts reaction of 5-aminopyrazole derivatives with cyclic ketimines attached to a neutral functional group is reported. This protocol allows the formation pyrazole-based C2-quaternary indolin-3-ones high enantioselectivities and regioselectivities. Moreover, gram-scale synthesis 5-aminopyrazole-based was performed, no decrease in yield enantioselectivity.

Язык: Английский

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Recent Advances in the Dearomative Skeletal Editing of Mono-azaarenes

Synthesis, Год журнала: 2023, Номер 56(01), С. 55 - 70

Опубликована: Янв. 17, 2023

Abstract Despite its challenges, the skeletal editing of mono-azaarenes (pyridines, quinolines, and isoquinolines) has shown unparalleled synthetic utility in construction complex molecules that are difficult to access by conventional methods. In this short review, we summarize three most recently developed strategies for deconstruction azaarene cores, with a focus on their generality, limitations, mechanistic aspects. Also, application strategy total synthesis some important natural products is discussed. 1 Introduction 2 Skeletal Editing Mono-Azaarenes through Zincke-like Reactions 3 Mono-azaarenes Aza-Buchner 4 via Photoinduced Radical or Energy-Transfer Processes 5 Conclusion

Язык: Английский

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