Dearomative ring expansion of thiophenes by bicyclobutane insertion

Science, Год журнала: 2023, Номер 381(6653), С. 75 - 81

Опубликована: Июль 6, 2023

Skeletal ring enlargement is gaining renewed interest in synthetic chemistry and has recently focused on insertion of one or two atoms. Strategies for heterocyclic expansion through small-ring remain elusive, although they would lead to the efficient formation bicyclic products. Here, we report a photoinduced dearomative thiophenes by bicyclo[1.1.0]butanes produce eight-membered rings under mild conditions. The value, broad functional-group compatibility, excellent chemo- regioselectivity were demonstrated scope evaluation product derivatization. Experimental computational studies point toward photoredox-induced radical pathway.

Язык: Английский

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Atroposelective Construction of Nine‐Membered Carbonate‐Bridged Biaryls

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(31)

Опубликована: Май 27, 2022

Abstract We herein demonstrated an efficient method for the atroposelective construction of nine‐membered carbonate‐bridged biaryls through vinylidene ortho ‐quinone methide (VQM) intermediates. Diverse products with desirable pharmacological features were synthesized in satisfying yields and good to excellent enantioselectivities. In subsequent bioassays, several agents showed considerable antiproliferative activity via mitochondrial‐related apoptosis mechanism. Further transformations produced more structural diversity may inspire new ideas developing functional molecules.

Язык: Английский

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Recent advances towards organocatalytic enantioselective desymmetrizing reactions

Trends in Chemistry, Год журнала: 2022, Номер 4(3), С. 191 - 205

Опубликована: Янв. 22, 2022

Язык: Английский

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Enantioselective Synthesis of Medium-Sized-Ring Lactones via Iridium-Catalyzed Z-Retentive Asymmetric Allylic Substitution Reaction

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(11), С. 4770 - 4775

Опубликована: Март 10, 2022

Medium-sized rings are important structural units, but their synthesis, especially in a highly enantioselective manner, has been great challenge. Herein we report an synthesis of medium-sized-ring lactones by iridium-catalyzed Z-retentive asymmetric allylic substitution reaction. The reaction features mild conditions and broad substrate scope. Various eight- to 11-membered-ring can be afforded moderate excellent yields (up 88%) enantioselectivity 99% ee). utilization both Z-allyl precursors Ir catalyst is critical for the formation.

Язык: Английский

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Phosphine‐Catalyzed Enantioselective (3+2) Annulation of Vinylcyclopropanes with Imines for the Synthesis of Chiral Pyrrolidines

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(24)

Опубликована: Март 31, 2022

A phosphine-catalyzed highly enantioselective and diastereoselective (up to 98 % ee >20 : 1 dr) (3+2) annulation between vinylcyclopropanes N-tosylaldimines has been developed, which allows facile access a range of functionalized chiral pyrrolidines. Notably, this method makes use as synthon for phosphine-mediated asymmetric reaction, will offer new opportunities potential applications cyclopropanes substrates in organic transformations.

Язык: Английский

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Skeletal Editing: Ring Insertion for Direct Access to Heterocycles

Molecules, Год журнала: 2024, Номер 29(9), С. 1920 - 1920

Опубликована: Апрель 23, 2024

Skeleton editing has rapidly advanced as a synthetic methodology in recent years, significantly streamlining the synthesis process and gaining widespread acceptance drug development. This field encompasses diverse ring reactions, many of which exhibit immense potential skeleton editing, facilitating generation novel skeletons. Notably, reactions that involve cleavage two distinct rings followed by reformation new through insertion play pivotal role construction article aims to compile systematize this category emphasizing primary reaction types offering thorough exploration their associated complexities challenges. Our endeavor is furnish readers with comprehensive strategies, igniting research interest injecting fresh impetus into advancement domain.

Язык: Английский

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Palladium-catalyzed selective C–C bond cleavage and stereoselective alkenylation between cyclopropanol and 1,3-diyne: one-step synthesis of diverse conjugated enynes

Chemical Science, Год журнала: 2022, Номер 13(9), С. 2692 - 2700

Опубликована: Янв. 1, 2022

Palladium-catalyzed tandem activation and functionalization of readily accessible cyclopropanols have been demonstrated to access valuable conjugated enynes from 1,3-diynes with high stereo-selectivity.

Язык: Английский

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An efficient approach to angular tricyclic molecular architecture via Nazarov-like cyclization and double ring-expansion cascade

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Апрель 28, 2022

A modular and efficient method for constructing angular tri-carbocyclic architectures containing quaternary carbon center(s) from 1,3-dicycloalkylidenyl ketones is established, which involves an unconventional synergistic cascade of a Nazarov cyclization two ring expansions. It features high selectivity, mild conditions convenient operation, wide scope easy availability substrate. Substitution with R1 R2 at the 4πe-system electron-donating group favors this reaction, while that electron-withdrawing or proton disfavors. The as directs initial expansion its own site, p-π- n-π- associated substituent selectively later near location because beneficial maintenance original conjugated system. stereoselectivity has proved to be governed by either steric effect R3 R4 expanded rings, migration ability migrating atom. Density Functional Theory calculation suggests would rate-determining step. racemic total synthesis natural (±)-waihoensene realized in 18 steps use methodology.

Язык: Английский

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Dearomative Insertion of Fluoroalkyl Carbenes into Azoles Leading to Fluoroalkyl Heterocycles with a Quaternary Center

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(1)

Опубликована: Ноя. 15, 2023

Abstract The skeletal ring expansion of heteroarenes through carbene insertion is gaining popularity in synthetic chemistry. Efficient strategies for heterocyclic to access heterocycles containing a fluoroalkyl quaternary carbon center are highly desirable because their broad applications medicinal Herein, we report general strategy the dearomative one‐carbon azoles using N ‐triftosylhydrazones as precursors, resulting ring‐expanded excellent yields with good functional‐group compatibility. generality this methodology late‐stage diversification pharmaceutically interesting bioactive molecules and versatile transformations products has been demonstrated.

Язык: Английский

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Asymmetric Catalytic Ring‐Expansion of 3‐Methyleneazetidines with α‐Diazo Pyrazoamides towards Proline‐Derivatives

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(32)

Опубликована: Июнь 15, 2023

We realized a highly efficient formal [1,2]-sigmatropic rearrangement of ammonium ylides generated from 3-methylene-azetidines and α-diazo pyrazoamides. The employ readily available chiral cobalt(II) complex N,N'-dioxide enabled the ring-expansion azetidines, affording variety quaternary prolineamide derivatives with excellent yield (up to 99 %) enantioselectivity % ee) under mild reaction condition. For ylides, installation pyrazoamide group as masked brick build scaffolds proved successful. enantioselective ring expansion process was elucidated by DFT calculations.

Язык: Английский

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