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

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(21), P. 11745 - 11753

Published: May 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.

Language: Английский

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

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(2), P. 386 - 399

Published: Jan. 21, 2022

Language: Английский

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Chemistry of 2-vinylindoles: synthesis and applications

New Journal of Chemistry, Journal Year: 2022, Volume and Issue: 46(28), P. 13383 - 13400

Published: Jan. 1, 2022

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

Language: Английский

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Asymmetric Catalytic Approaches Employing α,β‐Unsaturated Imines

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(15)

Published: Feb. 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.

Language: Английский

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

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(4), P. 108830 - 108830

Published: July 27, 2023

Language: 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, Journal Year: 2023, Volume and Issue: 59(39), P. 5902 - 5905

Published: Jan. 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).

Language: Английский

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

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 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.

Language: Английский

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

Chirality, Journal Year: 2022, Volume and Issue: 34(7), P. 1019 - 1034

Published: May 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.

Language: Английский

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

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(21), P. 3107 - 3110

Published: Jan. 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.

Language: 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, Journal Year: 2023, Volume and Issue: 25(26), P. 4776 - 4781

Published: June 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.

Language: Английский

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