Unexpected Copper-Catalyzed Cascade Reaction of 1,6-Enynes with Sulfoxonium Ylides

Organic Letters, Journal Year: 2022, Volume and Issue: 24(39), P. 7095 - 7100

Published: Sept. 26, 2022

An unprecedented copper-catalyzed cascade reaction of 1,6-enynes with sulfoxonium ylides is reported, providing a series structurally intriguing 2,3-disubstituted indolines bearing conjugated dienone functionality at the 3-position in moderate to excellent yields good chemo-, regio-, and diastereoselectivities under mild conditions. Importantly, sulfoxonium-ylide-derived copper-carbene herein exhibits quite different reactivity from that diazo copper-carbene. A rational mechanism, an initial ammonium ylide rather than allene formation, proposed.

Language: Английский

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Maleimide‐Controlled Formation of Indanonylpyrrolinediones and Spiroindanonylpyrrolinediones via Rh(III)‐Catalyzed C−H Activation of Sulfoxonium Ylides

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(24), P. 4595 - 4602

Published: Nov. 1, 2023

Abstract A substrate‐controlled [4+1] annulation of sulfoxonium ylides with maleimides via Rh(III)‐catalyzed C−H bond activation is developed. The reaction 2‐methyl‐ N ‐arylmaleimides in the presence AgNTf 2 diastereoselectively provides diversely functionalized indanonylpyrroline‐2,5‐dione derivatives. Furthermore, AgBF 4 , subsequent leads to biologically intriguing various spiroindanonylpyrroline‐2,5‐diones. This methodology offers a broad substrate scope, good functional group tolerance, and diastereoselectivity.

Language: Английский

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Base-Promoted Nucleophilic Phosphorylation of Benzyl Fluorides via C(sp³)–F Cleavage

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(16), P. 11739 - 11746

Published: Aug. 7, 2024

Herein, a transition-metal-free phosphorylation of benzyl fluorides with P(O)-H compounds is disclosed. In the presence

Language: Английский

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High-throughput experimentation and machine learning-promoted synthesis of α-phosphoryloxy ketones via Ru-catalyzed P(O)O-H insertion reactions of sulfoxonium ylides

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 10, 2024

Language: Английский

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Research Progress of Sulfoxonium Ylides in the Construction of Five/Six-Membered Nitrogen-Containing Heterocycles

Chinese Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 42(9), P. 2745 - 2745

Published: Jan. 1, 2022

Language: Английский

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Machine Learning and Quantum Calculation for Predicting Yield in Cu-Catalyzed P–H Reactions

Molecules, Journal Year: 2023, Volume and Issue: 28(16), P. 5995 - 5995

Published: Aug. 10, 2023

The paper discussed the use of machine learning (ML) and quantum chemistry calculations to predict transition state yield copper-catalyzed P–H insertion reactions. By analyzing a dataset 120 experimental data points, was determined using density functional theory (DFT). ML algorithms were then applied analyze 16 descriptors derived from chemical product yield. Among studied, Support Vector Machine (SVM) achieved highest prediction accuracy 97%, with over 80% correlation in Leave-One-Out Cross-Validation (LOOCV). Sensitivity analysis performed on each descriptor, comprehensive investigation reaction mechanism conducted better understand characteristics. Finally, model used plans for design, demonstrating strong predictive performance subsequent validation.

Language: Английский

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Gold-catalyzed redox cycloisomerization/nucleophilic addition/reduction: direct access to 2-phosphoryl indolin-3-ones

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(61), P. 8568 - 8571

Published: Jan. 1, 2022

An efficient gold(I)-catalyzed redox cycloisomerization/nucleophilic addition/reduction reaction of o-nitroalkynes with various H-phosphorus oxides is established. Through the intramolecular cyclization and subsequent intermolecular nucleophilic no external reactant, a variety arylphosphoryl alkylphosphoryl indolin-3-ones high functional-group compatibility are obtained in moderate to good yields. Mechanistic studies suggest that phosphorus nucleophiles mediate cleavage N-O bond as reductant.

Language: Английский

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Electrochemical synthesis of α-thiocyanato-α-carbonyl sulfoxonium ylides

Tetrahedron Letters, Journal Year: 2022, Volume and Issue: 109, P. 154165 - 154165

Published: Sept. 26, 2022

Language: Английский

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Copper‐Catalyzed α‐Arylation of Sulfoxonium Ylides Using Hypervalent Iodine Compounds

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 366(3), P. 396 - 401

Published: Dec. 9, 2023

Abstract A Cu(I)‐catalyzed synthesis of α‐arylated sulfoxonium ylides has been achieved from mesitylene‐derived diaryliodonium salts and α‐carbonyl ylides. The reaction is believed to proceed via an electrophilic Cu(III)‐aryl intermediate that can be trapped upon nucleophilic attack the ylide precursor. was tolerant both α‐keto α‐ester‐derived ylides, drug‐derived motifs electronically‐diverse arenes, enabled direct 32 α‐aryl‐sulfoxonium in 42–85% yield.

Language: Английский

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Ultraviolet-Light-Induced P–H Insertion of α-Halocarbenes

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

Published: Nov. 29, 2024

An intriguing P–H insertion of arylhalodiazirines with H-phosphorus oxides under ultraviolet-light irradiation is described. This methodology provides an efficient and straightforward route to the construction a variety α-halophosphorus in good yields (≤95%), which represents unique example α-halocarbenes for C–P bond formation. The metal-free protocol features advantages mild reaction conditions, high atom economy, environmental friendliness.

Language: Английский

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