Radical Brook rearrangement: past, present, and future

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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

Organic Letters, Journal Year: 2024, Volume and Issue: 26(28), P. 5911 - 5916

Published: July 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.

Language: Английский

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

Organic Letters, Journal Year: 2024, Volume and Issue: 26(10), P. 2141 - 2145

Published: March 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.

Language: Английский

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Visible-Light-Induced Insertion of Siloxycarbene into Amide N–H Bonds: Synthesis of Carbinolamides from Acylsilanes and Amides

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 90(4), P. 1727 - 1732

Published: Jan. 20, 2025

The insertion of carbene into secondary amide N-H bonds remains underexplored in organic synthesis. In this work, we discovered the visible-light-induced siloxycarbene bonds. This metal-free, facile reaction proceeds with atom economy under mild conditions a broad range amides, including benzanilide, acetanilide, oxindole, isatin, quinolinone, and maleimide, affording stable N- O-acetals excellent isolated yields. addition, chemoselective reveals robustness chemical transformation.

Language: 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, Journal Year: 2025, Volume and Issue: unknown, P. 5796 - 5805

Published: March 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.

Language: Английский

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Recent progress in synthetic strategies for novel β-lactams linked with five-membered heterocycles (N/O/S): advances in medicinal chemistry (2020–2025)

Medicinal Chemistry Research, Journal Year: 2025, Volume and Issue: unknown

Published: April 12, 2025

Language: Английский

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Cobalt-Catalyzed Diester Formation with CO at Atmospheric Pressure via Three-Component Reactions

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 28, 2025

We propose a cobalt-catalyzed three-component reaction conducted under mild conditions. Following the carbonyl insertion at atmospheric pressure, proceeds via nucleophilic attack by alcohols to form diesters. Notably, scope of reagents can be extended include range anilines. Furthermore, products this transformation serve as crucial synthetic building blocks for diverse organic synthesis processes, with subsequent derivatizations yielding promising results.

Language: Английский

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Visible-Light-Induced [2 + 2] Cyclization of Alkynes with Bromodifluoroacetylsilanes: Facile Access to gem-Difluorocyclobutenones

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 29, 2025

Language: Английский

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Remote Catalytic C(sp³)–H Alkylation via Relayed Carbenoid Transfer upon Olefin Chain Walking

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(45), P. 31114 - 31123

Published: Oct. 30, 2024

Transition metal carbenes have emerged as versatile intermediates for various types of alkylations. While reactions carbene species with alkenes been extensively studied, most examples focus on cyclopropanation and allylic C-H insertion. Herein, we present the first example a catalytic strategy carbene-involved regioselective remote alkylation internal olefins by synergistically combining two iridium-mediated reactivities olefin chain walking carbenoid migratory The method, utilizing sulfoxonium ylides bench-stable robust precursor, was found to be effective series tethered alkyl chains, heteroatom substituents, complex biorelevant moieties. Combined experimental computational studies revealed that reversible iridium hydride-mediated proceeds lead terminal alkyl-Ir intermediate, which then forms final insertion, resulting in terminal-alkylated products.

Language: Английский

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Photoinduced Copper‐Catalyzed Cross‐Coupling of Acylsilanes with Heteroarenes via Bimetallic Relay

Advanced Science, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 14, 2024

Abstract The transition metal‐catalyzed direct coupling reactions involving electron‐rich Fischer carbene species are largely underdeveloped and remain a big challenge. Here, reaction of azoles azine N ‐oxides is reported with copper bearing an α ‐siloxy group i, which can be in situ generated from acylsilanes catalytically under photoirradiation redox‐neutral conditions. This between Cu‐carbene hard carbanion nucleophiles may undergo bimetallic relay process, confirmed by the kinetic analysis NMR analysis. features mild conditions remarkable heterocycle compatibility. Notably, this protocol tolerates series azole or ‐oxide derivatives, including benzoxazole, benzothiazole, benzoimidazole, benzoisoxazole, oxazole, oxadiazole, triazolo[4,3 ‐a ]pyridine, purine, caffeine, pyridine ‐oxide, quinoline pyrazine pyridazine etc. synthetic value approach demonstrated efficient synthesis histamine h4 receptor ligand marketed drug carbinoxamine.

Language: Английский

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