Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

Chemical Reviews, Год журнала: 2022, Номер 122(24), С. 17479 - 17646

Опубликована: Окт. 14, 2022

Alkenes and their derivatives are featured widely in a variety of natural products, pharmaceuticals, advanced materials. Significant efforts have been made toward the development new practical methods to access this important class compounds by selectively activating alkenyl C(sp2)–H bonds recent years. In comprehensive review, we describe state-of-the-art strategies for direct functionalization sp2 C–H C–F until June 2022. Moreover, metal-free, photoredox, electrochemical also covered. For clarity, review has divided into two parts; first part focuses on currently available using different alkene as starting materials, second describes bond easily accessible gem-difluoroalkenes material. This includes scope, limitations, mechanistic studies, stereoselective control (using directing groups well metal-migration strategies), applications complex molecule synthesis where appropriate. Overall, aims document considerable advancements, current status, emerging work critically summarizing contributions researchers working fascinating area is expected stimulate novel, innovative, broadly applicable functionalizations coming

Язык: Английский

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Carbon–Carbon Bond Cleavage for Late-Stage Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(22), С. 12313 - 12370

Опубликована: Ноя. 9, 2023

Late-stage functionalization (LSF) introduces functional group or structural modification at the final stage of synthesis natural products, drugs, and complex compounds. It is anticipated that late-stage would improve drug discovery's effectiveness efficiency hasten creation various chemical libraries. Consequently, products a productive technique to produce product derivatives, which significantly impacts biology development. Carbon-carbon bonds make up fundamental framework organic molecules. Compared with carbon-carbon bond construction, activation can directly enable molecular editing (deletion, insertion, atoms groups atoms) provide more efficient accurate synthetic strategy. However, selective unstrained still one most challenging projects in synthesis. This review encompasses strategies employed recent years for cleavage by explicitly focusing on their applicability functionalization. expands current discourse reactions providing comprehensive overview types bonds. includes C-C(sp), C-C(sp2), C-C(sp3) single bonds; double triple bonds, focus catalysis transition metals organocatalysts. Additionally, specific topics, such as ring-opening processes involving three-, four-, five-, six-membered rings, are discussed, exemplar applications these techniques showcased context bioactive molecules discovery. aims shed light advancements field propose potential avenues future research realm

Язык: Английский

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Photoinduced arylative formal 4-endo-dig cyclization of propargyl alcohols/amines to access strained heterocycles

Green Chemistry, Год журнала: 2024, Номер 26(5), С. 2705 - 2711

Опубликована: Янв. 1, 2024

A novel synthetic strategy to access strained heterocycles is revealed through photocatalysed annulative formal 4- endo-dig cyclization of propargyl alcohols/amines with benzoquinones under catalyst/reagent-free conditions using non-hazardous solvent.

Язык: Английский

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Rhodium‐Catalyzed Dual C−H Activation for Regioselective Triple Annulation of Enaminones: Access to Polycyclic Naphthopyran Derivatives

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(11), С. 1770 - 1776

Опубликована: Март 21, 2023

Abstract Rh‐catalyzed C−H activation of arenes for oxidative annulations with alkynes stands out as a protocol polycyclic scaffolds. This perspective drives us to disclose herein rhodium catalyzed regioselective triple annulation enaminones hydroxyl‐alkynoates via double functionalization naphtho‐pyran Secondary coordination OH in alkynoate dictated the regioselectivity. Initial lactonization occurred chemoselectively on enamine part carbo rhodation followed by reductive elimination. was scalable and has shown high functionality tolerance. KIE studies were done get insight mechanism, some downstream transformations achieved show synthetic potential method.

Язык: Английский

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Recent Progress in Application of Propargylic Alcohols in Organic Syntheses

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(18), С. 2991 - 3019

Опубликована: Июль 14, 2023

Abstract Propargylic alcohols are readily available bifunctional (alkyne and hydroxyl groups) synthons, which recognize as one of the attractive synthetic feedstock in organic transformations. Especially, recent years employment these valuable molecules has frequently been observed literature. Hence, present review highlights advancements application propargylic cyclization, substitution, addition reactions.

Язык: Английский

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Pd-catalyzed regioselective rollover dual C–H annulation cascade: facile approach to phenanthrene derivatives

Chemical Communications, Год журнала: 2023, Номер 59(64), С. 9714 - 9717

Опубликована: Янв. 1, 2023

A Pd-catalyzed rollover cascade dual C–H annulation of aryl phenols with alkynols for producing phenanthrene scaffolds in a regioselective manner was developed. Necessary control, KIE and deuterium experiments were conducted to determine the reaction mechanism.

Язык: Английский

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Pd-Catalyzed Selective Arylative Cascade Cyclization of 1,6-Diynes and Dibenzoxaborins for Fused Naphthalene Derivatives

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 10, 2025

A palladium-catalyzed new mode of cascade arylative cyclization 1,6-diynes is disclosed using dibenzoxaborin as an arylating agent featuring transmetalation and selective migratory insertion the key steps. This process enables efficient construction polysubstituted fused naphthalene skeletons via formation three C-C bonds through dual regioselectivity in both arylation well C-H functionalization. Some control experiments kinetic isotope effect (KIE) studies were conducted to elucidate reaction mechanism, some product diversifications achieved showcase synthetic potential.

Язык: Английский

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Propargyl Alcohols as Bifunctional Reagents for Divergent Annulations of Biphenylamines via Dual C−H Functionalization/Dual Oxidative Cyclization

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(12)

Опубликована: Дек. 30, 2022

The C-H functionalization strategy provides access to valuable molecules that previously required convoluted synthetic attempts. Dual unsymmetrical functionalization, with a single bifunctional reagent, is an effective tactic. Propargyl alcohols (PAs), despite containing reactive C≡C bond, have not been explored as building blocks via oxidative cleavage. Annulations activation are versatile and synthetically attractive strategy. We disclose PA new reagent for dual of biphenylamine regioselectively annulated outcomes. On tuning the conditions, annulation bifurcated towards unusual cyclization. This method accommodates wide range PAs showcases late-stage diversification some natural products.

Язык: Английский

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Rh-catalyzed chemo-, stereo- and regioselective C–H cascade annulation of indolyloxopropanenitriles for pyranoindoles

Chemical Communications, Год журнала: 2023, Номер 59(67), С. 10137 - 10140

Опубликована: Янв. 1, 2023

Selective annulations of alkynes represent a powerful tool for constructing multicyclic scaffolds while installing desired substitution patterns with precision. Herein, we report Rh-catalyzed unique annulation indolyl oxopropanenitrile hydroxy-alkynoates to access pyranoindole cyclic motifs, featuring enol oxygen as rare chemoselective reactive terminal. The reaction proceeds via five-membered oxy-rodacycle through C-H activation by rhodium complex guided enolic- and propargyloxy dual co-ordination enable regio- stereoselective modular assembly.

Язык: Английский

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Chemoselective Oxypalladation of (o‐Alkynylaryl)amide‐Triggered Site‐Selective C−H Annulation for Stereoselective Synthesis of Succinimide‐Fused Polycycles

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер unknown

Опубликована: Март 20, 2024

Abstract We report herein a palladium‐catalyzed, site‐selective cyclative annulation of o ‐alkynyl arylamides with maleimide for the stereoselective construction succinimide‐fused benzoxazine derivatives. This operationally simple and modular protocol provides access to polycyclic frameworks. The other associated features are high functional group compatibility, gram‐scale synthetic potential, downstream transformations. Control labeling experiments were conducted get insights into mechanism.

Язык: Английский

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