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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Cobalt‐Catalyzed Enantioselective C−H Carbonylation towards Chiral Isoindolinones

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(10)

Опубликована: Янв. 11, 2024

Transition metal-catalyzed enantioselective C-H carbonylation with carbon monoxide, an essential and easily available C1 feedstock, remains challenging. Here, we disclosed unprecedented catalyzed by inexpensive readily cobalt(II) salt. The reactions proceed efficiently through desymmetrization, kinetic resolution, parallel affording a broad range of chiral isoindolinones in good yields excellent enantioselectivities (up to 92 % yield 99 ee). synthetic potential this method was demonstrated asymmetric synthesis biological active compounds, such as (S)-PD172938 (S)-Pazinaclone. resulting also serve ligands cobalt-catalyzed annulation alkynes construct phosphorus stereocenter.

Язык: Английский

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Oxygen‐Linked Cyclopentadienyl Rhodium(III) Complexes‐Catalyzed Asymmetric C−H Arylation of Benzo[h]quinolines with 1‐Diazonaphthoquinones

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(28), С. 15510 - 15516

Опубликована: Апрель 16, 2021

Abstract Chiral cyclopentadienyl rhodium (CpRh) complex‐catalyzed asymmetric C−H functionalization reactions have witnessed a significant progress in organic synthesis. In sharp contrast, the reported chiral Cp ligands are limited to C‐linked and often synthetically challenging. To address these issues, we developed novel class of tunable bearing oxygen linkers, which were efficient catalysts for arylation benzo[ h ]quinolines with 1‐diazonaphthoquinones, affording axially heterobiaryls excellent yields enantioselectivity (up 99 % yield, 98.5:1.5 er). Mechanistic studies suggest that reaction is likely proceed by electrophilic activation, followed coupling cyclometalated rhodium(III) complex 1‐diazonaphthoquinones.

Язык: Английский

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Rhodium‐Catalyzed Atroposelective Access to Axially Chiral Olefins via C−H Bond Activation and Directing Group Migration

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(1)

Опубликована: Окт. 22, 2021

Axially chiral open-chain olefins represent an underexplored class of platform. In this report, two classes tetrasubstituted axially acyclic have been accessed in excellent enantioselectivity and regioselectivity via C-H activation (hetero)arenes assisted by a migratable directing group en route to coupling with sterically hindered alkynes. The indoles bearing N-aminocarbonyl afforded C-N acrylamides the assistance racemic zinc carboxylate additive. DFT studies suggest β-nitrogen elimination-reinsertion pathway for migration. Meanwhile, employment N-phenoxycarboxamide delivered C-C enamides migration oxidizing group. Experiments that both cases (hetero)arene substrate adopts well-defined orientation during activation, which turn determines disposition alkyne migratory insertion. Synthetic applications representative are demonstrated.

Язык: Английский

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Sigma-Bond Metathesis as an Unusual Asymmetric Induction Step in Rhodium-Catalyzed Enantiodivergent Synthesis of C–N Axially Chiral Biaryls

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8417 - 8429

Опубликована: Март 23, 2023

Mechanistic understanding of asymmetric induction plays a crucial role in designing new catalytic reactions. Reported herein is atroposelective access to C-N axially chiral isoquinolones via rhodium-catalyzed C-H activation N-alkoxy benzamides and annulation with imidoyl sulfoxonium ylides. The coupling system proceeded excellent functional group tolerance, different conditions were identified afford one or the other enantiomeric product each enantioselectivity for representative class ylide reagent, thus making both enantiomers readily available using same catalyst. Experimental computational studies revealed pathway alkylation enantio-determining formal nucleophilic substitution-C-N cyclization that mediated by rhodium catalyst σ-bond metathesis as mechanism. Computational indicated solvent-dependent enatiodivergence originated from levels neutral versus cationic species.

Язык: Английский

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O-Allylhydroxyamine: A Bifunctional Olefin for Construction of Axially and Centrally Chiral Amino Alcohols via Asymmetric Carboamidation

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(14), С. 8150 - 8162

Опубликована: Апрель 4, 2023

Difunctionalization of olefins offers an attractive approach to access complex chiral structures. Reported herein is the design N-protected O-allylhydroxyamines as bifunctional that undergo catalytic asymmetric 1,2-carboamidation with three classes (hetero)arenes afford amino alcohols via C-H activation. The C═C bond in O-allylhydroxyamine activated by intramolecular electrophilic amidating moiety well a migrating directing group. carboamidation reaction pattern depends on nature (hetero)arene reagent. Simple achiral reacted give centrally β-amino excellent enantioselectivity. employment axially prochiral or racemic heteroarenes afforded both axial and central chirality enantio- diastereoselectivity. In case heteroarenes, coupling follows kinetic resolution s-factor up >600. A nitrene-based mechanism has been suggested based experimental studies, unique mode induction diastereoselectivity proposed. Applications alcohol products have demonstrated.

Язык: Английский

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Recent advances in the Rh-catalyzed cascade arene C–H bond activation/annulation toward diverse heterocyclic compounds

Organic & Biomolecular Chemistry, Год журнала: 2021, Номер 19(8), С. 1705 - 1721

Опубликована: Янв. 1, 2021

A review highlighting the advances in Cp*Rh(iii) catalysed cascade arene C–H activation/annulation including application, scope, limitations and mechanism of these transformations.

Язык: Английский

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Rhodium-Catalyzed Regio-, Diastereo-, and Enantioselective Three-Component Carboamination of Dienes via C–H Activation

ACS Catalysis, Год журнала: 2021, Номер 11(11), С. 6692 - 6697

Опубликована: Май 24, 2021

Reported herein is the rhodium-catalyzed enantioselective three-component coupling of arene, diene, and dioxazolone that occurs via C–H activation en route to allyl intermediate. This carboamination reaction affords chiral allylic amines in 1,2-selectivity, E-selectivity, enantioselectivity, with electrophilic amination π-allyl species being both regio- enantio-determining.

Язык: Английский

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Enantioselective Synthesis of Isoindolinone by Palladium-Catalyzed Aminoalkynylation of O-Phenyl Hydroxamic Ethers with Alkynes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(7), С. 4320 - 4326

Опубликована: Фев. 9, 2024

A highly efficient palladium-catalyzed asymmetric tandem aza-Heck/Sonogashira coupling reaction of O-phenyl hydroxamic ethers with terminal alkynes is described. This protocol enables versatile access to challenging chiral isoindolinone derivatives bearing a quaternary stereogenic center. The aminoalkynylation shows broad functional group tolerance and allows the straightforward preparation isoindolinones high efficiency excellent enantioselectivity under mild conditions. DFT calculations were performed disclose mechanism origins enantioselectivity.

Язык: Английский

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Chiral Allylic Amine Synthesis Enabled by the Enantioselective Cp^XRh(III)-Catalyzed Carboaminations of 1,3-Dienes

ACS Catalysis, Год журнала: 2021, Номер 11(4), С. 2279 - 2287

Опубликована: Фев. 5, 2021

Considering the importance of chiral allylic amine structural motif and rarity synthetic methods toward their construction, herein, we report a CpXRh(III)-catalyzed enantioselective intermolecular carboamination 1,3-dienes via N-phenoxy amides-derived aryl C–H activation intramolecular amide transfer. The methodology enables direct synthesis variety amines with embedment phenol functionalities proceeds under mild conditions sequential formation completely regioselective C–C bond highly C–N bond. Integrated experimental computational mechanistic studies reveal an unusual Rh(III)–Rh(I)–Rh(III) catalytic pathway, in which alkene insertion/π-allylation/intramolecular nucleophilic substitution cascade was involved for this transformation. Besides, application derivation natural products late-stage assembly bioactive complexes has also been demonstrated, further strengthens utility approach.

Язык: Английский

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