Visible Light-Promoted Regioselective Benzannulation of Vinyl Sulfoxonium Ylides with Ynoates

JACS Au, Journal Year: 2024, Volume and Issue: 4(3), P. 1073 - 1080

Published: March 1, 2024

Herein, we report a highly regioselective [4 + 2]-annulation of vinyl sulfoxonium ylides with ynoates under light-mediated conditions. The reaction proceeds through the new dienyl ylide, which undergoes photolysis blue light irradiation to give substituted naphthalene scaffolds. method presented here operates at room temperature and does not require addition an external photosensitizer. in situ-generated ylide absorbs acts as photosensitizer for formation arenes. synthetic potential these benzannulations was further illustrated by various transformations scale-up reaction. Moreover, control experiments quantum chemical calculations reveal mechanistic details developed

Language: Английский

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Metal-free cascade O–H double insertion between I^(III)/S^(VI)-ylides, carboxylic acids, and alcohols: modular access to unsymmetrical α,α-O,O-substituted ketones

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(11), P. 3234 - 3241

Published: Jan. 1, 2024

Herein, we present a cascade O–H double insertion reaction between I (III) /S (VI) -ylides, carboxylic acids, and alcohols under metal-free conditions, enabling the modular synthesis of unsymmetrical α,α- O , -substituted ketones.

Language: Английский

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A Platform for the Synthesis of Diverse Phosphonyl and Thiofunctionalized Sulfoxonium Ylides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(27), P. 5811 - 5816

Published: June 28, 2024

A practical strategy for the construction of diverse phosphonyl and thiofunctionalized sulfoxonium ylides via controllable monofunctionalization hybrid I(III)/S(VI) is presented. This process allows efficient P–H insertion under Cu catalysis, enabling synthesis ylides, whereas reaction with sulfur-containing reagents including AgSCF3, KSC(S)OR, KSCN mild conditions resulted in α-trifluoromethylthiolation, dithiocarbanation, thiocyanation accordingly. Of note, wide substrate compatibility (108 examples), excellent efficiency (up to 99% yield), gram-scale experiments, various product derivatizations highlight synthetic utility this protocol.

Language: Английский

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Discovery and synthesis of atropisomerically chiral acyl-substituted stable vinyl sulfoxonium ylides

Nature Chemistry, Journal Year: 2023, Volume and Issue: 16(1), P. 132 - 139

Published: Nov. 9, 2023

Language: Английский

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A Carbene Relay Strategy for Cascade Insertion Reactions

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 19, 2023

Abstract Insertion reactions that involve stabilized electrophilic metallocarbenes are of great importance for installing α‐heteroatoms to carbonyl compounds. Nevertheless, the limited availability carbene precursors restricts introduction only a single heteroatom. In this report, we describe new approach based on an I (III) /S (VI) reagent promotes cascade insertion heteroatoms. This is achieved by sequentially generating two α‐heteroatom‐substituted metal carbenes in one reaction. We found mixed ylide reacts efficiently with transition catalyst and X−H bond (where X=O, N). transformation leads sequential formation sulfoxonium‐ X‐substituted Rh‐carbenes, enabling further another Y−H bond. Remarkably, wide range symmetrical unsymmetrical α,α‐ O , ‐, N ‐subsituted ketones can be prepared under mild ambient conditions. addition, successfully demonstrated other cascades, such as CN/CN double amidation, C−H/C−S insertion, C−S/Y−H Y=S, N, O, C). Notably, latter cascades enabled simultaneous installation three functional groups α‐carbon compounds step. These demonstrate versatility our approach, allowing synthesis esters multiple using common precursor.

Language: Английский

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Divergent Construction of α,α-Difunctionalized Ketones via [1,2]-Sigmatropic Rearrangement/Alkylation-Hydroxylation/Dialkylation of I^(III)/S^(VI) Ylides

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

Published: April 1, 2025

The rare [1,2]-sigmatropic rearrangement of sulfoxonium-iodonium hybrid ylides is described, which enables the efficient sulfoxidation/sulfonylation-alkylation I(III)/S(VI) with 1,3-dicarbonyls. By slight modification reaction conditions, controllable alkylation-hydroxylation and dialkylation were achieved. This strategy affords a diverse array α,α-difunctionalized ketones in moderate to good yields, demonstrating broad substrate scope. These findings provide an important advancement sulfoxonium highlight divergent reactivity ylides.

Language: Английский

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Cyclic Sulfoxonium Ylides: Synthesis and Chemospecific Reactivity in the Catalytic Alkylation of Indoles

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(7)

Published: Feb. 7, 2023

Abstract The study of the reactivity cyclic sulfoxonium ylides has been so far neglected, in particular for reactions that forms carbon‐carbon bond at ylide carbon atom. Herein, we describe synthesis by palladium‐catalyzed intramolecular arylation and these C3‐alkylation indoles presence either an acid catalyst or iridium catalyst. This revealed catalysis is only efficient which tether a six‐membered lactone, whereas was better suited to reaction five‐membered ring ketone lactone. observed chemospecificity might be due relative basicity under steric hindrance around carbene intermediate when conducted with

Language: Английский

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Transformations based on direct excitation of hypervalent iodine(iii) reagents

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(6), P. 1577 - 1586

Published: Jan. 1, 2023

Hypervalent iodine compounds became an important class of reagents in synthesis. In this review, we present reactivity patterns five different structural classes hypervalent and their complexes under visible light irradiation.

Language: Английский

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Catalyst‐Free Direct Hydrocarbonation of Terminal Alkynes Toward E‐Alkene Substituted Stabilized Sulfoxonium Ylides

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: April 2, 2025

Amide and alkene moieties are frequently found in natural products privileged structures pharmaceuticals agrochemicals. Moreover, vinyl sulfoxonium ylide can be converted into a broad range of high-value compounds, thus they have been widely employed organic synthesis. However, the synthesis alkene-substituted amide-sulfoxonium ylides via intermolecular hydrocarbonation alkynes remains underexplored. This study describes development high-throughput approach to provide diverse functionalized E-alkene substituted (hetero)amide-sulfoxonium ylides. The reaction occurs under mild metal-free conditions, employing as highly effective nucleophiles, which participate Michael addition reactions with various alkynes, such esters, thioesters, ketones, amides, sulfones. low-cost, operationally simple has substrate scope, high functional group compatibility, excellent regio- stereoselectivity, making it suitable for transformation structurally complex molecules. Furthermore, obtained stabilized directly useful valuable 1,5-dicarbonyl thiabenzene 1-oxide compounds.

Language: Английский

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Isocyanide-Based Multicomponent Reaction: Cascade α-Acyloxylation/Carboxamidation and [3 + 1+1] Cyclization of I^(III)/S^(VI)-Ylides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(29), P. 6263 - 6268

Published: July 12, 2024

A metal-free cascade of α-acyloxylation/carboxamidation I(III)/S(VI)-ylides, carboxylic acids, and isonitriles via a Passerini-like multicomponent reaction is reported. Unexpectedly, [3 + 1+1] cyclization involving I(III)/S(VI)-ylides two molecules ethyl isocyanoacetate was observed. The strategy allows for the synthesis unsymmetrical α,α-disubstituted ketones functionalized pyrroles with up to 99% yield wide substrate compatibility. Notably, procedure has been extended late-stage modification drugs natural products, offering an elegant complement classic Passerini reaction.

Language: Английский

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