Electrocatalytic Access to Azetidines via Intramolecular Allylic Hydroamination: Scrutinizing Key Oxidation Steps through Electrochemical Kinetic Analysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(28), С. 15360 - 15369

Опубликована: Июль 10, 2023

Azetidines are prominent structural scaffolds in bioactive molecules, medicinal chemistry, and ligand design for transition metals. However, state-of-the-art methods cannot be applied to intramolecular hydroamination of allylic amine derivatives despite their underlying potential as one the most prevalent synthetic precursors azetidines. Herein, we report an electrocatalytic method sulfonamides access azetidines first time. The merger cobalt catalysis electricity enables regioselective generation key carbocationic intermediates, which could directly undergo C-N bond formation. mechanistic investigations including electrochemical kinetic analysis suggest that either catalyst regeneration by nucleophilic cyclization or second oxidation intermediate is involved rate-determining step (RDS) our protocol highlight ability electrochemistry providing ideal means mediate oxidation.

Язык: Английский

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Recent advances in the accessibility, synthetic utility, and biological applications of aziridines

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(22), С. 4553 - 4573

Опубликована: Янв. 1, 2023

Compounds featuring aziridine moieties are widely known and extensively reported in the literature. Due to their great potential from both synthetic pharmacological points of view, many researchers have focused efforts on development new methodologies for preparation transformation these interesting compounds. Over years, more ways obtain molecules bearing three-membered functional groups, which challenging due inherent reactivity, been described. Among them, several sustainable. In this review, we report recent advances biological chemical evolution derivatives, particular, variety described synthesis aziridines transformations leading formation such as 4-7 membered heterocycles pharmaceutical interest promising activities.

Язык: Английский

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EXPLORING AZETIDINE CONTAINING HETEROCYCLES: FROM GREEN SYNTHESIS TO APPLICATIONS

Tetrahedron, Год журнала: 2025, Номер unknown, С. 134491 - 134491

Опубликована: Янв. 1, 2025

Язык: Английский

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Hydrogen bond-promoted regio- and stereoselective synthesis of isoindoline derivatives through Pd-catalyzed isocyanide insertion reaction involving aziridines

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(6), С. 1775 - 1781

Опубликована: Янв. 1, 2024

We have successfully demonstrated an efficient and practical Pd-catalyzed reaction between aziridine isocyanide, leading to the synthesis of isoindoline derivatives in moderate good yields.

Язык: Английский

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Rapid sp³-Enriched Scaffold Generation via a Selective Aziridine Amide Ring-Opening Reaction

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(5), С. 3500 - 3508

Опубликована: Фев. 10, 2024

Sp

Язык: Английский

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Asymmetric Magnesium Catalysis for Important Chiral Scaffolds Synthesis

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(24), С. 4778 - 4800

Опубликована: Янв. 1, 2024

A review is presented of magnesium catalysis for the synthesis important chiral scaffolds. Several motifs that are present in classic ligands or natural products synthesized by Mg( ii ) catalytic methods briefly discussed.

Язык: Английский

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Metal-free anomalous [5+1] cycloaddition reactions of donor–acceptor aziridines for the synthesis of 2H-1,4-oxazines

Chemical Communications, Год журнала: 2023, Номер 59(55), С. 8572 - 8575

Опубликована: Янв. 1, 2023

A new type of metal-free [5+1] cycloaddition reaction donor-acceptor aziridines with 2-(2-isocyanoethyl)indoles is reported herein. This method exhibits broad substrate scope and atom-economy. series 2H-1,4-oxazines containing an indole heterocycle skeleton were obtained in up to 92% yield under mild conditions. Control experiments revealed that free N-H crucial for the above transformations. The theoretical calculation studies provided guidance on in-depth insight into mechanism hydrogen-bond between carbonyl group was identified lower energy barrier transition states.

Язык: Английский

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Organocatalyzed Enantioselective [2 + 2] Cycloaddition of C,N-Cyclic Ketimines and Allenoates

Organic Letters, Год журнала: 2023, Номер 26(1), С. 225 - 230

Опубликована: Дек. 26, 2023

We report a novel enantioselective and regioselective [2 + 2] cycloaddition of allenoate C,N-cyclic ketimine catalyzed by quinidine derivative. The methodology enables the synthesis fused tricyclic azetidines with quaternary stereogenic center exhibiting high enantioselectivities. broad range substrates demonstrates generality protocol, resulting functional products can be easily converted to variety valuable synthons. To elucidate plausible reaction mechanism how catalyst affects absolute stereocontrol over products, we conducted corresponding density theory (DFT) calculations.

Язык: Английский

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Asymmetric synthesis of complex tricyclo[3.2.2.0]nonenes from racemic norcaradienes: kinetic resolutionviaDiels–Alder reaction

Chemical Science, Год журнала: 2023, Номер 14(7), С. 1844 - 1851

Опубликована: Янв. 1, 2023

Herein, the enantioselective synthesis of complex tricyclo[3.2.2.0]nonenes through Diels-Alder reaction is reported. Utilizing racemic norcaradienes prepared from visible-light-mediated dearomative cyclopropanation m-xylene as dienes and enone derivatives dienophiles, overall process represents a kinetic asymmetric transformation in presence chiral cobalt(ii) N,N'-dioxide. High diastereo- enantioselectivity could be obtained most cycloaddition processes part racemization norcaradiene observed. The topographic steric maps catalysts were collected to rationalize relationship between reactivity with catalysts.

Язык: Английский

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Enantioselective [3+2] Cycloaddition of Donor‐Acceptor Aziridines and Imines to Construct 2,5‐trans‐Imidazolidines

Chemistry - A European Journal, Год журнала: 2023, Номер 29(18)

Опубликована: Янв. 5, 2023

An enantioselective [3+2] cycloaddition of donor-acceptor aziridines with N-aryl protected imines was developed a Ni(ClO4 )2 ⋅ 6H2 O/N,N'-dioxide catalyst system, providing broad range chiral trans-substituted imidazolidine compounds good yields and excellent enantioselectivities (up to 99 % yield, up 98 ee). Control experiments indicated that the products could offer diastereoselectivities control Ni(II)-N,N'-dioxide complex interaction substrates. The possible catalytic process proposed rationalize stereocontrol.

Язык: Английский

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