Recent Advances in Cyclization Reactions of 1,6‐Enynes

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(6), P. 1220 - 1268

Published: Jan. 22, 2024

Abstract Elaborated molecular architectures, specifically those bearing one or more carbon stereocenters, stand as an important class of carbocyclic and heterocyclic frameworks because they are frequently occurring core structures in numerous natural products biologically active pharmaceutical molecules. Over the past few decades, development versatile synthetic approaches via cascade cyclization reactions 1,6‐enynes for construction a series fused spiro compounds has been focus great deal research initiatives. These synthesis strategies peculiarly fascinating context assembly wide array molecules, products, agrochemicals, functional materials. In this review, recent developments transformations with diverse coupling reagents summarized since 2018, which could be divided into five categories: 1) Introduction; 2) Transition metal catalyzed 1,6‐enynes; 3) Metal‐free 4) Visible‐light‐induced 5) Electrocatalytic 1,6‐enynes.

Language: Английский

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Transition‐Metal‐Catalyzed Transformations Involving the Heck Reaction

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(15), P. 2436 - 2466

Published: June 12, 2023

Abstract Elaborated molecular architectures including complex carbocycles, heterocycles, and polycyclic structures represent an important class of organic compounds because they are ubiquitous structural units in a broad variety biologically pharmacologically relevant natural products, medicinal molecules, functional materials. A major challenge modern synthetic methodology is the development strategically efficient selective construction these from readily available starting Transition‐metal‐catalyzed transformations involving Heck reaction as pivotal step have afforded powerful approach for accessing sophisticated skeletons set easy‐to handle materials, thus highlighting its potential significance streamlining drug discovery process. Over past few decades, significant effort has been devoted to derivatives versatile routes, number direct strategies reported. In this review, latest advances transition‐metal‐catalyzed critical summarized, which could be divided into six categories: 1) Heck/Sonogashira tandem reaction; 2) Heck/Suzuki 3) Heck/Heck 4) Heck/Hiyama 5) Heck/Cacchi 6) Heck/C−H bond functionalization reaction.

Language: Английский

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Enantioselective Synthesis of Hydrindanes via Palladium-Catalyzed Asymmetric Desymmetrization of Cyclohexadiene Derivatives

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

Published: Feb. 5, 2025

We herein disclose a strategy for the asymmetric desymmetrization of cyclohexadiene derivatives via palladium-catalyzed Heck and tandem Heck/Tsuji-Trost allylic alkoxylation reaction. By employing DCE as solvent, we obtained variety chiral hydrindanes containing an all-carbon quaternary carbon center tertiary in good yields with excellent enantioselectivities. With alcohols valuable one stereocenter two centers were constructed high level enantioinduction.

Language: Английский

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Palladium-Catalyzed Cascade Carbonylation Reaction To Construct Ester Derivatives

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 24, 2025

We have developed a palladium-catalyzed ester carbonylation reaction that enables the synthesis of ester-substituted benzofuran derivatives in single step through introduction alkyl halides undergoing situ hydrolysis and alkynyl aryl iodides. This method demonstrates broad applicability to both primary secondary while maintaining excellent functional group compatibility under low palladium loading conditions. Notably, this strategy significantly expands scope reactions.

Language: Английский

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Palladium-Catalyzed Asymmetric Desymmetrization for the Simultaneous Construction of Chiral Phosphorus and Quaternary Carbon Stereocenters

Organic Letters, Journal Year: 2024, Volume and Issue: 26(28), P. 5934 - 5939

Published: July 5, 2024

A palladium-catalyzed asymmetric tandem Heck and carbonylation of bisallyl-phosphine oxides has been developed. This desymmetrization process provided an efficient route to the simultaneous synthesis a chiral P-stereogenic center quaternary carbon stereocenter in good yields with diastereo- enantioselectivities.

Language: Английский

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Enantioconvergent synthesis of axially chiral amides enabled by Pd-catalyzed dynamic kinetic asymmetric aminocarbonylation

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 23, 2024

Atropisomeric biaryls bearing carbonyl groups have attracted increasing attention due to their prevalence in diverse bioactive molecules and crucial role as efficient organo-catalysts or ligands asymmetric transformations. However, preparation often involves tedious multiple steps, the direct synthesis via carbonylation has scarcely been investigated. Herein, we report an palladium-catalyzed enantioconvergent aminocarbonylation of racemic heterobiaryl triflates with amines dynamic kinetic transformation (DyKAT). This protocol features a broad substrate scope excellent compatibility for rapid construction axially chiral amides good high yields enantioselectivities. Detailed mechanistic investigations discover that base can impede intramolecular hydrogen bond-assisted axis rotation products, thus allowing success achieve enantioselectivity. Moreover, achieved be directly utilized N,N,N-pincer copper-catalyzed enantioselective formation C(sp3)-N C(sp3)-P bonds. Axially containing not only exist various drug candidates but also serve authors transformation.

Language: Английский

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Enantioselective Synthesis of Bicyclo[3.2.1]octadienes via Palladium‐Catalyzed Intramolecular Alkene‐Alkyne Coupling Reaction

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(51)

Published: Nov. 3, 2023

Bicyclo[3.2.1]octadiene compounds and derivatives exist in a number of natural products bioactive compounds. Nevertheless, catalytic enantioselective protocols for the synthesis these skeletons have not been disclosed. Herein we reported palladium-catalyzed asymmetric intramolecular alkene-alkyne coupling alkyne-tethered cyclopentenes, affording library enantionenriched bicyclo[3.2.1]octadienes excellent yields enantioselectivities (mostly >99 % ee). Moreover, could undergo an unusual iodination-induced 1,2-acyl migration, forming iodinated with three vicinal stereocenters. The enone isolated olefin motifs embedded provide useful handles downstream elaboration.

Language: Английский

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Construction of Benzofuran‐3(2H)‐one Scaffolds bearing a C2 Quaternary Center via Palladium‐Catalyzed Carbonylative Heck Reaction using Mo(CO)6 as Carbonyl Source

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: July 2, 2024

Abstract A Pd‐catalyzed carbonylative Heck reaction of 2‐iodophenyl alkenyl ether using Mo(CO) 6 as a safe CO source has been developed. This research provides an atom‐economic and straightforward route for the efficient construction benzofuran‐3(2 H )‐one scaffolds with C2 quaternary center in moderate to good yields, which features operational safety, functional group compatibility easy scale‐up.

Language: Английский

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Palladium-Catalyzed Four-Component Radical Cascade Carbonylation Access to 2,3-Disubstituted Benzofuran Derivatives

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 24, 2024

Multicomponent radical tandem reactions have emerged as a crucial technique for synthesizing complex molecules in organic chemistry. In this study, we report palladium-catalyzed four-component difluoroalkylative carbonylation of enynes and ethyl difluoroiodoacetate. This transformation proceeds through multistep sequential reaction that introduces reactive difluoro carbonyl groups while constructing the benzofuran skeleton. Moreover, variety valuable 2,3-disubstituted derivatives were obtained respectable yields with excellent functional group compatibility.

Language: Английский

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New Synthetic Approaches for the Construction of Enantioenriched Molecules Bearing Quaternary Stereocenters

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(21), P. 4294 - 4322

Published: Aug. 17, 2024

Abstract Optically active molecule architectures stand as an important class of organic compounds and occupy a key role in academic industrial communities. Particularly, the molecules bearing quaternary carbon are vital importance because its favorable conformation valuable three‐dimensional molecules, which frequently play broad spectrum functional materials, pharmaceutical relevant natural agrochemicals. Over past few decades, large number synthetic strategies for enantioselective construction with chiral centers have been focus research initiatives. In this review, state‐of‐the‐art toward synthesis enantioenriched stereocenters summarized, could be segmented into four categories: 1) Construction optically by addition to prochiral sp 2 carbon; 2) all‐carbon via substitution at non‐chiral tetra‐substituted 3) kinetic resolution; 4) desymmetrization reactions.

Language: Английский

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