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

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(5), P. 2705 - 2711

Published: Jan. 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.

Language: Английский

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Electrochemical Synthesis of Spirolactones from α-Tetralone Derivatives with Methanol as a C1 Source

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 5016 - 5020

Published: June 3, 2024

Spirolactones are widely found in pharmaceuticals and bioactive natural products. However, efficient environmentally friendly approaches to accessing spirolactones still highly desirable. Herein, a novel electrochemical synthesis of from α-tetralone derivatives with methanol as C1 source is described. This reaction exhibits high efficiency good functional group tolerance.

Language: Английский

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ortho‐Selective Suzuki Coupling of Dichlorophenol and Dichlorobenzylalcohol in Water under Palladium Catalysis Directed by Noncovalent Interactions and Computational Analysis

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

Published: Jan. 14, 2025

Abstract The use of attractive noncovalent interactions is emerging as a versatile approach to address site‐selectivity challenges. Herein, we report ortho‐selective Suzuki coupling reactions in water 2,3‐dichloroarenes and 2,4‐dichloroarenes bearing hydroxy group the presence palladacycle catalyst directed by interactions. Various ortho‐substituted arylphenols arylbenzyl alcohols were obtained good excellent yields with high selectivity. Density functional theory (DFT) calculations ab initio molecular dynamics (AIMD) simulations suggested that ortho ‐selective dichlorophenols dichlorobenzyl occurred through electrostatic hydrogen bonding interactions, respectively.

Language: 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, Journal Year: 2025, Volume and Issue: unknown

Published: April 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.

Language: Английский

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Construction of Rings via Metal‐Catalyzed C−H Annulation with Unsymmetrical Internal Alkynes: Selectivity and Applications

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(21)

Published: Aug. 19, 2023

Abstract Selective and concise construction of ring systems that are ubiquitous skeletons across chemistry, drugs materials, is indispensable for human life. Of note, directed C−H annulation with alkynes the expedient delivery holds great importance, featuring step‐ atom‐economy, mild conditions, broad substrate scope. However, regioselectivity issues remained when using unsymmetrical annulation. Herein, we summarized recent achievements towards solving this problem by developing directing groups, metal catalysts, versatile traceless functionality ensure overall regioselectivity, enantioselectivity, efficiency, synthetic application. We hope concept will promote further development precise functional molecules alkynes.

Language: 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, Journal Year: 2024, Volume and Issue: unknown

Published: March 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.

Language: Английский

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Diversity-Oriented Synthesis of Indole-Fused Polycyclic Scaffolds via Rhodium-Catalyzed NH-Indole-Directed C–H Coupling of 2-Phenyl-1H-indoles with Propargylic Alcohol Derivatives

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(8), P. 5589 - 5605

Published: April 5, 2024

Diversity-oriented synthesis strategy for the efficient assembly of indole-fused polycyclic scaffolds via rhodium-catalyzed NH-indole-directed C–H coupling with propargylic alcohol derivatives in a regioselective manner was developed. Five 2-phenyl-1H-indole-embedded core skeletons were synthesized. In particular, three different exo-olefin-containing polycycles realized, which may be manipulated further chemistry.

Language: Английский

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Pd‐Catalyzed Vicinal Intermolecular Annulations of Iodoarenes, Indoles, and Carbazoles with Enynes

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(7)

Published: Nov. 6, 2023

Reaching the formidable C-H corners has been one of top priorities organic chemists in recent past. This prompted us to disclose herein a vicinal annulation 2-iodo benzoates, indoles, and carbazoles with N-embedded 1,6-enynes through 7-/8-membered palladacycles. The relay does not require assistance any directing group, leading multicyclic scaffolds, which are readily diversified an array adducts (with new functional tethers and/or three contiguous stereocenters), we showcase rare benzylic mono-oxygenation.

Language: Английский

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Conjugated Olefin Enabled Rollover Cyclometallation of Distant C‐H Bonds: Regioselective Annulation of o‐Alkenyl Phenols with Alkynes

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(70)

Published: Oct. 11, 2023

Although challenging, the distant C-H functionalization with precision is quite rewarding and has long been intriguing. Tailoring an appropriate template accomplishes job but prerequisite sets limitation. We herein unveil our discovery of annulation alkynes on to two (from directing group) bonds through rollover cyclometallation assisted by conjugated C=C bond. The follows a concomitant cyclization rare triple functionalization. totally regioselective array unsymmetrical alkynes, taking leverage extended conjugation or tertiary hydroxyl co-ordination. mechanism supported control experiments, KIE & labelling studies Mass spectrometry.

Language: Английский

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Transition metal-free and temperature dependent one-pot access to phenanthrene-fused heterocycles via a 1,3-dipolar cycloaddition pathway

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(92), P. 13755 - 13758

Published: Jan. 1, 2023

A versatile, operationally simple, temperature-dependent, and transition metal-free one-pot protocol has been devised for the preparation of novel phenanthrene-fused pyrazoles. Notably, overall process involved an intermolecular condensation, intramolecular 1,3-dipolar cycloaddition, aromatization sequence starting from biaryl-2,2'-aldehydes bearing enoate esters with various hydrazine hydrochlorides. sequential three-component operation also achieved. Importantly, it was shown that this amenable to hydroxylamine hydrochloride as nitrogen source furnished isoxazoles. temperature dependent nature demonstrated, which led formation dealkoxylcarbonylated pyrazoles at slightly higher temperatures longer reaction times. Remarkably, effectively constructed two C-N bonds one C-C bond exhibited a broad substrate scope.

Language: Английский

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