Hydroxyl-Directed Ru(II)-Catalyzed Synthesis of Fused Dihydrofurans Using 1,4-Dioxane and Sulfoxonium Ylides as Annulating Agents

Organic Letters, Journal Year: 2023, Volume and Issue: 25(1), P. 215 - 219

Published: Jan. 3, 2023

An unprecedented annulation reaction is developed for the synthesis of dihydrofuran-fused compounds. In this Ru-catalyzed hydroxyl-group-directed reaction, easily affordable sulfoxonium ylides and 1,4-dioxane were used as annulating partners. This first example use a methylene source to construct heterocyclic scaffold. A wide range dihydrofuran0fused coumarins naphthalenes synthesized using three-component reaction.

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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Overview of Transition Metal Catalyzed Multicomponent Reactions Based on Trapping of Allylic Electrophiles

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(4)

Published: Jan. 11, 2024

Abstract Multicomponent reactions provide an excellent approach toward quaternary carbon centres utilizing convergent chemical in a highly selective manner under one‐pot conditions. The reactivity of substrates and metal catalysts is carefully controlled, precluding the formation side‐products. In this context, transition catalyzed onium ylides generated via diazo precursors nucleophiles with third component (an electrophile) have garnered significant attention. Using allylic precursor as electrophilic partner provides opportunities to construct all‐carbon centres. Furthermore, presence allyl fragment multicomponent product serves pivotal handle for carrying out subsequent modifications. Several recent studies employed Rh, Pd, dual Rh/Pd catalytic systems involving alkylation that proceed synergistic or relay pathway. Although not significantly successful, few cases, asymmetric induction achieved through chiral phosphoric acids phosphine ligands. Limited substrate catalyst scope underlying mechanistic complexities posed formidable challenges, slowing advancement reactions. This review details using readily available like compounds, carbonates, (R‐OH, R‐NH 2 , etc .) forming complex organic compounds. Our primary objective discuss issues may facilitate progress field.

Language: Английский

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Copper-Mediated Cyclization of Terminal Alkynes with CF₃-Imidoyl Sulfoxonium Ylides To Construct 5-Trifluoromethylpyrroles

Organic Letters, Journal Year: 2024, Volume and Issue: 26(11), P. 2249 - 2254

Published: March 7, 2024

A copper-mediated [3 + 2] cyclization of CF3-imidoyl sulfoxonium ylides and terminal alkynes has been demonstrated. This work provides a practical approach for assembling 5-trifluoromethylpyrroles with the merits broad substrate scope, good functional tolerance, mild reaction conditions. Control experiments DFT studies indicate that this may involve addition π-bonds by copper-carbene radicals hydrogen migration.

Language: Английский

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Synthetic Strategies to Control C–N Atropisomerism in Acyclic Amines and Amides

Synthesis, Journal Year: 2023, Volume and Issue: 55(16), P. 2427 - 2438

Published: Feb. 21, 2023

Abstract Atropisomeric molecules are a privileged class of stereogenic material that have important applications in catalysis, materials science and medicines. To date, the majority work has been focused upon biaryl heterobiaryl scaffolds involving restricted rotation between pair cyclic fragments, but C–N atropisomeric based amines amides, where nitrogen atom is not part ring system, rapidly emerging as an molecules. This focus this Short Review, which begins by discussing factors influence configurational stability such provides historical background to their synthesis. followed detailed discussion state-of-the-art catalytic asymmetric strategies now available access C–Nacyclic atropisomers including carboxamides, sulfonamides, sulfinamides, phosphamides diarylamines. A variety different synthetic approaches discussed, kinetic resolution/desymmetrization, amination, C–H functionalization, N-functionalization, annulation. 1 Introduction 2 Atropisomerism Acyclic Amines Amides 3 Synthesis Directed Chiral Auxiliary 4 Atropselective 4.1 Kinetic Resolution Desymmetrization 4.2 Electrophilic Amination 4.3 Functionalization 4.4 N-Functionalization 4.5 Annulation 5 Conclusions Outlook

Language: Английский

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Brønsted Acid-Catalyzed Reaction of N-arylnaphthalen-2-amines with Quinone Esters for the Construction of Carbazole and C–N Axially Chiral Carbazole Derivatives

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(5), P. 2841 - 2850

Published: Feb. 22, 2023

We demonstrated here an efficient synthetic method of carbazole derivatives from readily available N-arylnaphthalen-2-amines and quinone esters catalyzed by Brønsted acid. With this strategy, a series were obtained in good to excellent yields (76 >99) under mild conditions. Large scale reaction illustrated the utility protocol. Meanwhile, C-N axially chiral also constructed moderate (36-89% yield) with atroposelectivities (44-94% ee) using phosphoric acid as catalyst, which provides novel strategy for atroposelective construction compounds new member atropisomers.

Language: Английский

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C–N Axially Chiral Heterobiaryl Skeletons Construction via Cobalt-Catalyzed Atroposelective Annulation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(28), P. 5191 - 5196

Published: July 10, 2023

Herein, the atroposelective construction of five-six heterobiaryl skeleton-based C-N chiral axis has been successfully accomplished via a Co-catalyzed C-H bond activation and annulation process, in which isonitrile was employed as C1 source 8-aminoquinoline moiety served both directing group integral part atropisomers, respectively. This conversion can be effectively carried out an environmentally friendly oxygen atmosphere, generating target axial heterobiaryls with excellent reactivities enantioselectivities (up to >99% ee) absence any additives, obtained 3-iminoisoindolinone products five membered N-heterocycle exhibit high atropostability. Additionally, axially monophosphine backbones derived from this protocol possess potential become alternative ligand platform.

Language: Английский

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Catalytic Enantioselective [4+1]-Annulation of Carboxylic Acids with Cyclopropenes

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

Published: Feb. 12, 2025

An efficient asymmetric synthesis of 3-vinylphthalides has been accomplished through rhodium-catalyzed [4+1]-annulation arylcarboxylic acids with cyclopropenes involving C–H bond functionalization. The method exhibited excellent compatibility for various functional groups and offered diverse substituted in yield enantioselectivity. Synthetic application control experiments were also performed to demonstrate the utility understand reaction pathway.

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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