Asymmetric Dearomatization of Indoles with Azodicarboxylates via Cascade Electrophilic Amination/Aza-Prins Cyclization/Phenonium-like Rearrangement

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(21), С. 11745 - 11753

Опубликована: Май 19, 2023

Herein, we report a highly efficient synthesis of enantioenriched aza-[3.3.1]-bicyclic enamines and ketones, class structural cores in many natural products, via asymmetric dearomatization indoles with azodicarboxylates. The reaction is initiated by electrophilic amination followed aza-Prins cyclization/phenonium-like rearrangement. A newly developed fluorine-containing chiral phosphoric acid displays excellent activity promoting this cascade reaction. absence or presence water as the additive directs pathway toward either enamine ketone products high yields (up to 93%) enantiopurity 98% ee). Comprehensive density functional theory (DFT) calculations reveal energy profile origins enantioselectivity water-induced chemoselectivity.

Язык: Английский

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Chemo-, regio- and enantioselective dearomative (3+2) reaction of non-functionalized 1-naphthols

Chem Catalysis, Год журнала: 2022, Номер 2(2), С. 386 - 399

Опубликована: Янв. 21, 2022

Язык: Английский

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Asymmetric Catalytic Approaches Employing α,β‐Unsaturated Imines

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(15)

Опубликована: Фев. 8, 2023

Abstract Nitrogen‐containing heterocyclic compounds have consistently been a noticeable center of attention due to their significant utilization in the domain synthetic organic chemistry, agrochemicals, and pharmaceuticals. α,β‐Unsaturated imines or conjugated provide lot cyclic as well acyclic products through reacting with versatile family compounds. This review summarizes recent advances enantioselective reactions α,β‐unsaturated by using methodologies for synthesizing various nitrogen‐containing heterocycles that contain four six‐membered rings. The synthesis rarely found seven‐, eight‐ nine‐membered also reported.

Язык: Английский

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Catalytic asymmetric dearomative azo-Diels–Alder reaction of 2-vinlyindoles

Chinese Chemical Letters, Год журнала: 2023, Номер 35(4), С. 108830 - 108830

Опубликована: Июль 27, 2023

Язык: Английский

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Chemistry of 2-vinylindoles: synthesis and applications

New Journal of Chemistry, Год журнала: 2022, Номер 46(28), С. 13383 - 13400

Опубликована: Янв. 1, 2022

In this review we shed the light of chemistry 2-vinylindoles, synthesis and application via metal coupling catalysis as a green approach.

Язык: Английский

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Catalytic asymmetric de novo construction of 4-pyrrolin-2-ones via intermolecular formal [3+2] cycloaddition of azoalkenes with azlactones

Chemical Communications, Год журнала: 2023, Номер 59(39), С. 5902 - 5905

Опубликована: Янв. 1, 2023

The chiral phosphoric acid-catalyzed asymmetric intermolecular formal [3+2] cycloaddition of azoalkenes with azlactones has been established. This convergent protocol leads to a facile and enantioselective de novo construction wide range fully substituted 4-pyrrolin-2-ones bearing carbon atom in good yields excellent enantioselectivities (26 examples, 72-95% 87-99% ee).

Язык: Английский

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Organocatalyzed asymmetric dearomative 1,3‐dipolar cycloaddition of 2‐nitrobenzofurans and N‐2,2,2‐trifluoroethylisatin ketimines

Chirality, Год журнала: 2022, Номер 34(7), С. 1019 - 1034

Опубликована: Май 6, 2022

Abstract A readily available chiral cyclohexanediamine‐derived bifunctional tertiary amine‐squaramide catalyst is more effective for the asymmetric dearomative 1,3‐dipolar cycloaddition of 2‐nitrobenzofurans and N ‐2,2,2‐trifluoroethylisatin ketimines. range structurally diverse spiro‐fused polyheterocyclic compounds containing oxindole, pyrrolidine, hydrobenzofuran motifs were smoothly obtained in excellent results (up to 99% yield, >20:1 dr all cases up ee). This method features high efficiency, mild reaction conditions, exquisite induction, wide functional group tolerance, great potential scale‐up synthesis, attractive product diversification.

Язык: Английский

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Catalytic [2,3]-sigmatropic rearrangement of sulfonium ylides derived from azoalkenes: non-carbenoid Doyle–Kirmse reaction

Chemical Communications, Год журнала: 2023, Номер 59(21), С. 3107 - 3110

Опубликована: Янв. 1, 2023

The Sc(III)-catalyzed [2,3]-sigmatropic rearrangement of sulfonium ylides derived from azoalkenes has been established. Owing to the absence a carbenoid intermediate, this protocol represents first non-carbenoid variant Doyle-Kirmse reaction. Under mild conditions, variety tertiary thioethers have readily prepared in good excellent yields.

Язык: Английский

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Catalytic Asymmetric Rearrangement of Azoalkene-Derived Sulfonium Ylides via Remote Chirality Control

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 26, 2025

The [2,3]-sigmatropic rearrangement has been widely utilized to construct C-S bonds. Herein, we report an enantioselective, intermolecular, and noncarbenoid of sulfonium ylides using azoalkenes. This process features a broad substrate scope, high efficiency, excellent enantioselectivity, achieving yields up 99% enantiomeric excess (ee) 96%. Furthermore, the protocol demonstrated good scalability.

Язык: Английский

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Chemo- and Diastereoselective Synthesis of Spirooxindole-pyrazolines and Pyrazolones via P(NMe₂)₃-Mediated Substrate-Controlled Annulations of Azoalkenes with α-Dicarbonyl Compounds

Organic Letters, Год журнала: 2023, Номер 25(26), С. 4776 - 4781

Опубликована: Июнь 26, 2023

P(NMe2)3-mediated substrate-controlled annulations of azoalkenes with α-dicarbonyl compounds are reported, where the serve as either four or five-atom synthons chemoselectively. The azoalkene participates in annulation isatins a four-atom synthon to furnish spirooxindole-pyrazolines, whereas it functions novel aroylformates, thereby leading chemo- and stereoselective formation pyrazolones. synthetic utilities have been demonstrated, TEMPO-mediated decarbonylation reaction is unveiled.

Язык: Английский

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