Recent developments on 1,2-difunctionalization and hydrofunctionalization of unactivated alkenes and alkynes involving C–S bond formation

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(5), С. 1322 - 1345

Опубликована: Янв. 1, 2023

Functionalization of alkenes/alkynes is a highly effective route to achieve molecular complexity. This review summarizes recent progresses on the 1,2-difunctionalization/hydrofunctionalization unactivated with C−S bond formation.

Язык: Английский

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Palladium‐Catalyzed Fluorinative Bifunctionalization of Aziridines and Azetidines with gem‐Difluorocyclopropanes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(42)

Опубликована: Авг. 12, 2023

Abstract An unprecedented Pd‐catalyzed fluorinative bifunctionalization of aziridines and azetidines was successfully developed via regioselective C−C C−F bond cleavage gem‐difluorocyclopropanes, leading to various β,β′‐bisfluorinated amines β,γ‐bisfluorinated amines. This reaction achieved by incorporating a 2‐fluorinated allyl group fluorine atom scissored from gem‐difluorocyclopropane in 100 % economy for the first time. The mechanistic investigations indicated that underwent amine attacking palladium complex generate η 2 ‐coordinated N‐allyl aziridine followed fluoride ligand transfer affording final β‐ γ‐fluorinated

Язык: Английский

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Modular and stereoselective synthesis of tetrasubstituted vinyl sulfides leading to a library of AIEgens

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Дек. 15, 2021

Abstract Tetraarylethylenes exhibit intriguing photophysical properties and sulfur atom frequently play a vital role in organic photoelectric materials biologically active compounds. Tetrasubstituted vinyl sulfides, which include both tetrasubstituted alkenes motifs, might be suitable skeleton for the discovery of new material molecules drug with unique functions properties. However, how to modular synthesis these kinds compounds is still challenging. Herein, chemo- stereo-selective Rh(II)-catalyzed [1,4]-acyl rearrangements α-diazo carbonyl thioesters has been developed, providing strategy library 63 sulfides. In this transformation, yield up 95% turnover number 3650. The mechanism reaction investigated by combining experiments density functional theory calculation. Moreover, “aggregation-induced emission” effect sulfides were also investigated, useful material, biological imaging chemicalnsing via structural modification.

Язык: Английский

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Highly Stereoselective Synthesis of Tetrasubstituted Vinyl Selenides via Rhodium-Catalyzed [1,4]-Acyl Migration of Selenoesters and Diazo Compounds

Organic Letters, Год журнала: 2022, Номер 24(11), С. 2175 - 2180

Опубликована: Март 14, 2022

Herein, we disclose a highly stereoselective Rh(II)-catalyzed 1,4-acyl rearrangement of selenium esters and α-diazo carbonyl compounds, which provides an efficient method for synthesizing tetrasubstituted vinyl selenides. Furthermore, this reaction also offers synthetic tool medium large ring compounds.

Язык: Английский

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TfOH-Catalyzed Regioselective S–H Insertion of Cyclic Thioamide Derivatives with Diazo Compounds at Room Temperature

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(7), С. 4452 - 4457

Опубликована: Март 28, 2023

We have developed a method for highly regioselective S–H bond insertion reactions of various diazo compounds and cyclic thioamide derivatives at room temperature. These provide straightforward access to alkylated benzimidazoles, benzothiazoles, benzoxazoles. This mild uses readily available TfOH as catalyst features broad substrate scope, good functional group tolerance, excellent yields, high regioselectivities.

Язык: Английский

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Organophosphorus-Catalyzed “Dual-Substrate Deoxygenation” Strategy for C–S Bond Formation from Sulfonyl Chlorides and Alcohols/Acids

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(13), С. 8628 - 8635

Опубликована: Июнь 9, 2023

A green method to construct C-S bonds using sulfonyl chlorides and alcohols/acids via a PIII/PV═O catalytic system is reported. The organophosphorus-catalyzed umpolung reaction promotes us propose the "dual-substrate deoxygenation" strategy. Herein, we adopt strategy, which achieves deoxygenation of synthesize thioethers/thioesters driven by redox cycling. represents an operationally simple approach stable phosphine oxide as precatalyst shows broad functional group tolerance. potential application this protocol demonstrated late-stage diversification drug analogues.

Язык: Английский

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Stereoselective synthesis of chiral sultam-fused dihydropyridinones via photopromoted NHC catalyzed [4 + 2] annulation

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(19), С. 5191 - 5196

Опубликована: Янв. 1, 2022

A photopromoted NHC catalyzed asymmetric [4+2] annulation of saccharine-derived azadienes and α -diazoketones was developed, affording the corresponding sultam-fused dihydropyridinones efficiently (up to 80% yield, 99% ee >20 : 1 d.r.).

Язык: Английский

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Comparison of the Efficiency of B–O and B–C Bond Formation Pathways in Borane-Catalyzed Carbene Transfer Reactions Using α-Diazocarbonyl Precursors: A Combined Density Functional Theory and Machine Learning Study

ACS Catalysis, Год журнала: 2024, Номер 14(19), С. 14486 - 14496

Опубликована: Сен. 16, 2024

Lewis acidic boranes, especially tris(pentafluorophenyl)borane [B(C

Язык: Английский

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TBAI-Catalyzed S–H and N–H Insertion Reactions of α-Diazoesters with Thiophenols and Amines under Metal-Free Conditions

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(16), С. 10990 - 10999

Опубликована: Авг. 2, 2022

Mild, convenient, and effective TBAI-catalyzed S–H N–H insertion reactions of α-diazoesters with thiophenols aromatic amines under metal-free conditions have been described, furnishing a straightforward general platform for the synthesis various thioethers 2-amino-2-oxoacetates in moderate to excellent yields. Moreover, this strategy features simple operation, mild conditions, broad substrate scope, easy scale-up.

Язык: Английский

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Solvent‐free, B(C₆F₅)₃‐Catalyzed S−H Insertion of Thiophenols and Thiols with α‐Diazoesters

Chemistry - An Asian Journal, Год журнала: 2022, Номер 17(16)

Опубликована: Июнь 9, 2022

Abstract Described herein is a B(C 6 F 5 ) 3 ‐catalyzed S−H insertion reaction of thiophenols and thiols with α‐diazoesters to access valuable α‐thioesters. With the established protocol, an array α‐thioester products are generated in moderate good yields broad scope functional group tolerance. In addition, this maintains its high efficiency on gram scale product can be easily transformed into other useful motifs. This proceeds under solvent‐free conditions at room temperature, generally finishes twenty minutes upon magnet stirring, which offers expedient way for synthesis thioether‐containing compounds.

Язык: Английский

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