Pd‐Catalyzed Dearomatization of Anthranils with Vinylcyclopropanes by [4+3] Cyclization Reaction

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(17), С. 5739 - 5743

Опубликована: Фев. 27, 2019

Abstract Dearomatization of anthranils with vinylcyclopropanes (VCPs) by Pd‐catalyzed [4+3] cyclization reaction has been realized. In the presence a catalytic amount borane as an activator, bridged cyclic products were obtained in good to excellent yields stereoselectivities. By introducing chiral PHOX ligand ( L5 ), asymmetric dearomatization reactions proceeded enantioselectivity. Borane plays key role for reactivity, likely owing formation borane–anthranil complex which confirmed NMR experiments.

Язык: Английский

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Copper‐Catalyzed Azide–Ynamide Cyclization to Generate α‐Imino Copper Carbenes: Divergent and Enantioselective Access to Polycyclic N‐Heterocycles

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(41), С. 17984 - 17990

Опубликована: Июль 4, 2020

Here an efficient copper-catalyzed cascade cyclization of azide-ynamides via α-imino copper carbene intermediates is reported, representing the first generation carbenes from alkynes. This protocol enables practical and divergent synthesis array polycyclic N-heterocycles in generally good to excellent yields with broad substrate scope diastereoselectivities. Moreover, asymmetric azide-ynamide has been achieved high enantioselectivities (up 98:2 e.r.) by employing BOX-Cu complexes as chiral catalysts. Thus, this constitutes example azide-alkyne cyclization. The proposed mechanistic rationale for further supported theoretical calculations.

Язык: Английский

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Highly Diastereo- and Enantioselective Synthesis of Tetrahydrobenzo[b]azocines via Palladium-Catalyzed [4 + 4] Cycloaddition

ACS Catalysis, Год журнала: 2021, Номер 11(5), С. 2684 - 2690

Опубликована: Фев. 12, 2021

The construction of N-heterocyclic eight-membered rings with good regio-, stereo-, and enantioselective control remains a formidable challenge in asymmetric catalysis. Herein, we report palladium-catalyzed [4 + 4] cycloaddition anthranils γ-methylidene-δ-valerolactones the presence Et3B, delivering highly functionalized tetrahydrobenzo[b]azocine derivatives high efficiency diastereoselectivities enantioselectivities (up to 92% yield, 20:1 dr, 99% ee). Moreover, complex substrates derived from natural products (bearing different functionalities) could be well-tolerated catalytic cycloaddition. mild reaction conditions, conjunction broad substrate scope (44 examples), level stereoselectivity, provide great potential build azocine compounds simple building blocks.

Язык: Английский

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Copper‐Catalyzed Enantioselective Doyle–Kirmse Reaction of Azide‐Ynamides via α‐Imino Copper Carbenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(10)

Опубликована: Янв. 14, 2023

[2,3]-Sigmatropic rearrangement reaction involving sulfonium ylide (Doyle-Kirmse reaction) generated from metal carbenes represents one of the powerful methods for construction C(sp3 )-S and C-C bonds. Although significant advances have been achieved, asymmetric versions via generation ylides rarely reported to date, they so far limited diazo compounds as carbene precursors. Here, we describe a copper-catalyzed enantioselective Doyle-Kirmse azide-ynamide cyclization, leading practical divergent assembly an array chiral [1,4]thiazino[3,2-b]indoles bearing quaternary carbon stereocenter in generally moderate excellent yields enantioselectivities. Importantly, this protocol unique catalytic non-diazo approach unprecedented [2,3]-sigmatropic α-imino carbenes.

Язык: Английский

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Isoxazoles as efficient alkyne amination reagents in divergent heterocycle synthesis

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review summarizes the latest trends and developments of isoxazole-enabled alkyne amination reactions their applications in divergent heterocycle synthesis.

Язык: Английский

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N-Pyridinyl Sulfilimines as a Source for α-Imino Gold Carbenes: Access to 2-Amino-Substituted N-Fused Imidazoles

Organic Letters, Год журнала: 2019, Номер 21(6), С. 1598 - 1601

Опубликована: Фев. 26, 2019

Gold-catalyzed formal 1,3-dipolar annulation between readily accessible N-pyridinylsulfilimines and ynamides is reported. A diverse set of imidazole derivatives prepared from the corresponding sulfilimines ynamides. These functionalized cyclic products can undergo further transformations to afford frameworks. Moreover, in situ synthesis feasible shows good potential nucleoside analogues.

Язык: Английский

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Synthesis of 2-Aminoindoles through Gold-Catalyzed C–H Annulations of Sulfilimines with N-Arylynamides

Organic Letters, Год журнала: 2019, Номер 21(11), С. 4327 - 4330

Опубликована: Май 22, 2019

A new gold-catalyzed C–H annulation of sulfilimines with N-phenylynamides is presented. As key intermediates this operationally simple reaction, the in situ generated α-imino gold carbenes insert into ortho bonds phenyl groups to afford 2-aminoindoles bearing a variety substitution patterns high selectivities. This reaction offers facile approach biologically important by using inexpensive and readily available starting materials.

Язык: Английский

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Gold‐Catalyzed Oxidative Alkyne Functionalization by N−O/S−O/C−O Bond Oxidants

Advanced Synthesis & Catalysis, Год журнала: 2020, Номер 362(18), С. 3664 - 3708

Опубликована: Май 11, 2020

Abstract Since the beginning of this century, homogeneous gold‐catalyzed alkyne transformations have been an active area research in pursuit developing efficient synthetic methodologies. This emerging which at exploited mild Lewis acid character gold and its propensity to form π‐complex with alkyne, has reinvigorated upon discovery oxidative functionalization 2007. The oxidation enabled direct access α‐oxo carbenes alkynal complex versatile reactivity applied achieve including but not limited oxyarylation, C−H, X−H (X=N, O) insertion, cyclization, cycloaddition, ring expansion, various cascade reactions. review provides a comprehensive summary methods, applications mechanistic insight by N−O/S−O/C−O bond oxidants covering literature reports appeared since magnified image

Язык: Английский

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Anthranils: versatile building blocks in the construction of C–N bonds and N-heterocycles

Organic Chemistry Frontiers, Год журнала: 2020, Номер 7(9), С. 1177 - 1196

Опубликована: Янв. 1, 2020

This review article provides an overview of the recent progress in transformations anthranils, which have emerged as versatile building blocks assembly various C–N bonds and medicinally active heterocyclic systems.

Язык: Английский

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Gold catalysis in quinoline synthesis

Chemical Communications, Год журнала: 2024, Номер 60(55), С. 6999 - 7016

Опубликована: Янв. 1, 2024

Quinolines are biologically and pharmaceutically important N-heterocyclic aromatic compounds, which have broad applications in medicinal chemistry. Thus, their efficient synthesis has attracted extensive attention, a range of synthetic strategies been established. Of note, gold-catalyzed methodologies for the quinolines greatly advanced this field. Various intermolecular annulation reactions, such as annulations aniline derivatives with carbonyl compounds or alkynes, anthranils based on A

Язык: Английский

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