Radical Brook rearrangement: past, present, and future

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review aims to provide an overview of radical Brook rearrangement, which is organized by grouping three type reactive species generated via the unique rearrangement process.

Язык: Английский

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Stereoselective Synthesis of Silyl Enol Ethers with Acylsilanes and α,β-Unsaturated Ketones

Organic Letters, Год журнала: 2024, Номер 26(28), С. 5911 - 5916

Опубликована: Июль 8, 2024

Acylsilanes are emerging bench-stable reagents for the generation of electron-rich oxycarbenes that difficult to access with unstable diazo compounds. Herein, we report a siloxycarbene-mediated stereoselective synthesis silyl enol ethers through visible-light-induced intermolecular reactions between acylsilanes and α,β-unsaturated ketones. Both solvent low temperature important success reaction. This approach features atomic economics, exclusive stereocontrol, broad substrate scope. The synthetic potential this methodology is demonstrated by gram-scale reaction various downstream transformations including requiring configuration purity ethers.

Язык: Английский

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Pd-Catalyzed Divergent Site-Selective Difluoromethylation and Difluoromethylcarbonylation of Aryl Sulfonium Salts

ACS Catalysis, Год журнала: 2024, Номер 14(18), С. 13557 - 13566

Опубликована: Авг. 28, 2024

The incorporation of the difluoromethyl (CF2H) group into arenes has increasingly been recognized as important in drug discovery. Herein, we report a divergent cross-coupling method for constructing both aryl difluoromethanes and difluoroketones from thianthrenium salts. Site selectivity Negishi-type coupling C1 insertion reactions was achieved under palladium catalysis. Both transformations proceed with broad functional tolerance, enabling late-stage difluoromethylation difluoromethylcarbonylation complex molecules. synthetic utility this demonstrated by synthesizing four pharmaceutical analogues same precursor applying it downstream functionalization difluoroketones.

Язык: Английский

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Direct C(sp3)-H functionalization with aryl and alkyl radicals as intermolecular hydrogen atom transfer (HAT) agents

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Recent years have witnessed the emergence of direct intermolecular C(sp

Язык: Английский

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Palladium-Catalyzed Addition of Trifluoroacetylsilanes to Alkenes and Allenes via the Cleavage of C–Si Bonds

Organic Letters, Год журнала: 2024, Номер 26(10), С. 2141 - 2145

Опубликована: Март 5, 2024

The palladium-catalyzed addition of trifluoroacetylsilanes to alkenes and allenes via the cleavage C–Si bonds is reported. When are used, cyclopropanation occurs afford cyclopropane derivatives bearing CF3 siloxy groups with a high degree stereoselectivity. silylacylation form alkenylsilane trifluoroacetyl group at allylic position complete regioselectivity. Both reactions allow for highly atom-economical access densely functionalized fluorinated organosilane using simple building blocks.

Язык: Английский

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From S-Fluoroalkylation to Fluoroalkylation–Thiolation: Difunctionalization of Alkenes with Fluoroalkyl Phenyl Sulfones and Thiophenols Enabled by Photoredox Copper Catalysis

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 17, 2025

Molecules containing fluoroalkyl and arylthio groups play a pivotal role in pharmaceutical agrochemical development. The simultaneous introduction of these functional through the 1,2-difunctionalization alkenes is an efficient strategy. Fluoroalkyl phenyl sulfones serve as accessible radical precursors; however, their tendency to interact with thiophenol via electron donor–acceptor interaction mechanism can impede desired transformation. Through meticulous selection solvent base, we successfully utilized copper catalysis facilitate alkene-involved three-component reaction. Our work unveils photoredox copper-catalyzed fluoroalkylation–thiolation using various (such perfluoroethyl, tetrafluoroethyl, trifluoromethyl, difluoromethyl, difluoroalkyl, difluorobenzyl). efficacy this approach exemplified by synthesis Kengreal derivatives.

Язык: Английский

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Synthesis of α-SF₅ Ketones by Oxypentafluorosulfanylation of Alkynes with SF₅Cl and Oxygen

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 18, 2025

Herein for the first time, we disclose a practical and straightforward approach to access α-SF5 ketones via direct oxypentafluorosulfanylation of alkynes with SF5Cl oxygen under acidic conditions by one step. The protocol features mild reaction conditions, broad substrate scope, good functional group compatibility can be applied late-state functionalization complex natural products pharmaceuticals. A radical mechanism involving SF5 addition triple bonds followed O2 capture is proposed.

Язык: Английский

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Asymmetric Trapping of Siloxyketenes In Situ Generated from [1,3]-Silyl Migration of α-Ketoacylsilanes: A Visible-Light-Driven Palladium-Catalyzed [4 + 2] Cycloaddition

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 5796 - 5805

Опубликована: Март 25, 2025

The transition metal-catalyzed asymmetric [n + 2] cycloaddition reaction with oxy-substituted ketene intermediates remains a synthetic challenge due to the limited availability of suitable precursors. Herein, we report visible-light-driven, palladium-catalyzed [4 vinyl benzoxazinanones siloxyketene intermediates, generating structurally diverse chiral quinolinone derivatives satisfactory diastereo- and enantioselectivities. transient generation siloxyketenes from α-ketoacylsilylanes through visible-light-induced Brook rearrangement is important for success present cycloaddition. 13C-labeling experiments reveal pathway involving [1,3]-silyl migration process. side arm effects BOX ligand silyl steric hindrance α-ketoacylsilanes play crucial roles in stereoselectivity control, theoretical calculations provide insights into stereochemical outcome reaction.

Язык: Английский

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Condition‐Controlled Selective Synthesis of CF₃‐Chromene and CF₃‐Benzofuran from N‐Phenoxyacetamide and CF₃‐Ynone

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 27, 2025

Comprehensive Summary Presented herein is a condition‐controlled selective synthesis of CF 3 ‐chromene and ‐benzofuran based on the reaction N ‐phenoxyacetamide ‐ynone. When carried out in MeOH under catalysis Rh(III), formed via C—H metalation‐initiated alkenylation, acetamide group migration intramolecular oxo ‐nucleophilic addition. On other hand, when run DMSO promotion CsOAc, generated aza ‐Michael addition‐initiated [3,3]‐σ rearrangement, addition water elimination. To our knowledge, this first report construction chromene or benzofuran scaffold along with introduction unit from same starting materials. The methodology was scalable products could be readily transformed into valuable products. Moreover, thus obtained possess decent anticancer activity.

Язык: Английский

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Water-Involved 1,3-Aminoxylation of Fluoroalkenes: Chemo-, Regio-, and Stereoselective Synthesis of β-Fluoroacyl Vinylamines

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

Опубликована: Апрель 9, 2025

Perfluoroalkyl alkenyl iodides (PFAIs) are emerging as highly reactive, storage-stable, and multifunctional fluoroalkyl-bearing reagents, facilitating the manufacture of value-added organofluorides through multi-halo-functionalization. Herein, we developed a water-involved 1,3-aminoxylation PFAIs with sulfonamides for chemo-, regio-, Z-stereoselective synthesis valuable β-fluoroacyl vinylamines. This reaction proceeded via sequential deiodoamination defluoroxylation process under transition-metal-free conditions, featuring broad substrate scope good functional group tolerance. Compared to reported methods, some drawbacks, such multistep manipulation, harsh need expensive catalysts, use toxic/sensitive could be eliminated. Furthermore, synthetic potential this method was demonstrated scale-up synthesis, postfunctionalization complex molecules, ready transformation products.

Язык: Английский

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