Benzyl Deuteriodifluoromethyl Sulfoxide: An Easily Accessible and Stable Reagent for Direct Deuterodifluoromethylthiolation

Organic Letters, Год журнала: 2024, Номер 26(3), С. 687 - 691

Опубликована: Янв. 18, 2024

A new, stable and scalable reagent based on a sulfoxide skeleton for direct deuteriodifluoromethylthiolation has been developed. The displays excellent reactivities toward Tf2O promoted C–H of electron-rich arenes, indoles, alkenes, intramolecular lactonization 2-alkynylbenzoates. Moreover, high deuteration rates good to yields were achieved under metal-free reaction conditions. As result, wide range deuteriodifluoromethylthilolated compounds prepared, enabling further applications in drug discovery.

Язык: Английский

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Stereoselective Synthesis of Polysubstituted Conjugated Dienes Enabled by Photo‐Driven Sequential Sigmatropic Rearrangement

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(24)

Опубликована: Апрель 8, 2024

We here reported a highly stereoselective method for the synthesis of polysubstituted conjugated dienes from α-aryl α-diazo alkynyl ketones and pyrazole-substituted unsymmetric aminals under mild conditions, which was promoted by photo-irridation involved with 1,6-dipolar intermediate quadruple sigmatropic rearrangements, successfully developed. In this transformation, cleavage four bonds recombination five were implemented in one operational step. This protocol provided modular tool constructing amines, pyrazoles α-alkynyl-α-diazoketones one-pot manner. The results mechanistic investigation indicated that plausible reaction path underwent 1,6-sigmatropic rearrangement instead 1,5-sigmatropic rearrangement.

Язык: Английский

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Truce‐Smiles Rearrangement of Diaryliodonium Salts in Ionic Liquids

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(28)

Опубликована: Май 17, 2023

The Truce-Smiles rearrangement is an intramolecular SN Ar reaction, enabling the formation of a new arene carbon-carbon bond with sufficiently strong carbon-centered nucleophile. Reported here are ortho-tosylmethylene functionalized diaryliodonium salts, which can undergo unprecedented in ionic liquids, resulting sulfonyl-substituted ortho-iodo diarylmethanes as powerful class building blocks chemical synthesis. protocol features aryliodo moiety hyper nucleofuge, facilitating Meisenheimer complex within migratory system.

Язык: Английский

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Defluorinative Multi‐Functionalization of Fluoroaryl Sulfoxides Enabled by Fluorine‐Assisted Temporary Dearomatization

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(36)

Опубликована: Июль 17, 2023

Owing to its unique physical properties, fluorine is often used open up new reaction channels. In this report, we establish a cooperation of [5,5]-rearrangement and fluorine-assisted temporary dearomatization for arene multi-functionalization. Specifically, the fluoroaryl sulfoxides with β,γ-unsaturated nitriles generates an intriguing dearomatized sulfonium species which short-lived but exhibits unusually high electrophilicity thus can be instantly trapped by nucleophiles dienes at remarkably low temperature (-95 °C) produce four types valuable multi-functionalized benzenes, respectively, involving appealing processes defluorination, desulfurization, sulfur shift. Mechanistic studies indicate that use on arenes not only circumvents generally inevitable [3,3]-rearrangement also impedes undesired rearomatization process, provides precious space constructing elaborating temporarily fluorinated species.

Язык: Английский

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β-Trifluorosulfinylesters: tuneable reagents for switchable trifluoromethylsulfinylation and C–H trifluoromethylthiolation

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(9), С. 2186 - 2192

Опубликована: Янв. 1, 2023

β-Trifluorosulfinylesters, a family of novel reagents from commercially available starting materials for direct trifluoromethylthiolation and trifluoromethylsulfinylation were developed.

Язык: Английский

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ortho-Cyanomethylation of aryl fluoroalkyl sulfoxides via a sulfonium–Claisen rearrangement

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(7), С. 1495 - 1499

Опубликована: Янв. 1, 2024

The sulfonium–Claisen rearrangement of aryl fluoroalkyl sulfoxides with acetonitrile enables the simultaneous incorporation a cyanomethyl group and fluoroalkylthio into arenes.

Язык: Английский

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Gold-Catalyzed 1,2-Rearrangement on Benzene Triggered by a Transient Dearomative Claisen Rearrangement

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 10, 2025

1,2-Migration on arenes represents a powerful transformation, because of its chemical skeleton and exit vector editing ability. However, the corresponding dearomative mediated 1,2-migration arene was ignored for decades, despite tremendous effort being devoted to develop reaction, which mainly capitalized breaking planarity three-dimensional diversification. Here, we report gold-catalyzed 1,2-rearrangement benzene by transient dearomatization high-resonance energy benzene. This functional transposition strategy enabled rapid access several precursors extended π-conjugated molecules, showcasing potential applications in materials sciences.

Язык: Английский

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Stereodivergent E- and Z-selective Sulfonium [3,3]-Rearrangement Enabled by Brønsted Bases

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 7, 2025

The stereoselective synthesis of (Z/E)-α-aryl α,β-unsaturated carbonyl compounds remains a significant synthetic challenge. Recently, we demonstrated novel Z-selective α-arylation nitriles via Morita-Baylis-Hillman-type sulfonium [3,3]-rearrangement. In this study, report that switching the base from K2CO3 to 4-methoxypyridine in final elimination step reverses stereochemistry products Z- E-geometry. Consequently, E/Z-divergent was achieved through these rearrangements. Additionally, mechanistic studies reveal weak interactions such as hydrogen bonding, n-π or π-π interactions, and short-range steric repulsions play crucial roles determining reaction.

Язык: Английский

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Ortho-Hydroxy-Substituted Diaryliodonium Salts Enabled Intramolecular Aryliodonium Rearrangement in Synthesis of Ortho-Iodo Diaryl Ethers

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

Опубликована: Апрель 15, 2025

A new family of ortho-hydroxy-substituted diaryliodonium salts was synthesized with 1-acetoxy-2-iodobenzenes, in which the acetyl group cleaved a one-pot synthesis. The ortho-hydroxyl-substituted underwent further intramolecular aryl migration reaction, giving ortho-iodo diaryl ethers either or without presence bases.

Язык: Английский

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Claisen rearrangement enabled efficiently access to biaryl phenols

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This study introduces an innovative method for C2-arylation of hydroxypyranones through a reductive iodonio-Claisen rearrangement, which enables the efficient synthesis biaryl phenols by integrating with tandem Claisen rearrangement sequence.

Язык: Английский

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