Copper‐Catalyzed Asymmetric Radical 1,2‐Alkylesterification of 1,3‐Dienes with Cycloalkyl Hydroperoxides and Acids

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(23)

Published: Oct. 17, 2023

Abstract Transition‐metal‐catalyzed radical relay cross‐coupling reactions of 1,3‐dienes have recently emerged as one the most powerful methods for construction structurally diverse allylic compound in a single chemical step. However, there still has been limited success expanding substrate scope precursors and coupling partners, well exploring catalytic asymmetric variants. Herein, we report copper‐catalyzed enantioselective three‐component 1,2‐alkylesterification using cycloalkyl hydroperoxides carbonyl‐containing alkyl sources carboxylic acids O‐nucleophiles under mild redox‐neutral conditions. This protocol features broad good functional group tolerance with respect to each component, providing practical access variety distally keto‐functionalized esters high enantioselectivity. Mechanistic studies suggest involvement sequential C−O this reaction.

Language: Английский

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FeCl₂-Mediated Rearrangement of Aminoperoxides into Functionalized Tetrahydrofurans: Dynamic Non-innocence of O-Ligands at an Fe Center Coordinates a Radical Cascade

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 27, 2024

The selective reaction of cyclic aminoperoxides with FeCl2 proceeds through a sequence O–O and C–C bond cleavages, followed by intramolecular cyclization, yielding functionalized tetrahydrofurans in 44–82% yields. Replacing the peroxyacetal group peroxide structure peroxyaminal fragment fundamentally alters pathway. Instead producing linear ketones, this modification leads to formation hard-to-access substituted tetrahydrofurans. Although aminoperoxide cores undergo multiple scissions, cascade is atom-economical. Computational analysis shows that O-ligands at Fe center have enough radical character promote fragmentation subsequent cyclization. stereoelectronic flexibility oxygen, combined iron's capacity stabilize reactive intermediates during multistep cascade, explains efficiency new atom-economic rearrangement.

Language: Английский

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Iron-catalyzed alkoxyl radical-mediated C–C bond cleavage/phosphorothiolation: a new approach to functionalized S-alkyl phosphorothioates

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(28), P. 5855 - 5860

Published: Jan. 1, 2023

A cheap iron-catalyzed alkoxyl radical-mediated C–C bond cleavage/phosphorothiolation cascade is presented. This protocol features mild and redox neutral conditions, wide substrate scope easy scalability.

Language: Английский

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Chemoselective and Divergent Synthesis of Chlorohydrins and Oxaheterocycles via Ir-Catalyzed Asymmetric Hydrogenation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(37), P. 6875 - 6880

Published: Sept. 11, 2023

Chlorohydrins and oxaheterocycles are synthetically valuable building blocks for diverse natural products therapeutic substances. A highly efficient Ir/f-phamidol-catalyzed asymmetric hydrogenation of ω-chloroketones was successfully developed, various chlorohydrins were obtained divergently with excellent yields enantioselectivities (up to >99% yield ee). Synthetic utilities this divergent transformation demonstrated by gram-scale synthesis key intermediates several enantiomerically enriched drugs via catalytic methodology.

Language: Английский

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Bioinspired Fe(II)‐Mediated Halogenative C−C Bond Activation of Ozonides: Temporary Installment of a Peroxide Bridge Allows Selective C−C Scissions for Replacement of a Carbonyl Group by a Halogen

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(23), P. 4190 - 4197

Published: Oct. 17, 2023

Abstract A selective reaction of bridged ozonides with Fe(II) salts proceeds through the sequence O−O, C−C scissions and halogenation to form α‐halogen substituted δ‐ketoesters δ‐diketones in 15–72% yields. The overall shows how a temporary installation peroxide functionality can be used replace acyl group within an acetoacetic ester unit halogen.

Language: Английский

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Synthesis of ω-Chloroalkyl Aryl Ketones via C–C Bond Cleavage of tert-Cycloalkanols with Tetramethylammonium Hypochlorite

Molecules, Journal Year: 2024, Volume and Issue: 29(8), P. 1874 - 1874

Published: April 19, 2024

An oxidative C–C bond cleavage of tert-cycloalkanols with tetramethylammonium hypochlorite (TMAOCl) has been developed. TMAOCl is easy to prepare from hydroxide, and the combination AcOH effectively promoted in a two-phase system without additional phase-transfer reagents. Unstrained were transformed into ω-chloroalkyl aryl ketones moderate excellent yields under metal-free mild reaction conditions.

Language: Английский

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Functional Group Transformation Via Carbonyl Derivatives

Elsevier eBooks, Journal Year: 2023, Volume and Issue: unknown

Published: Jan. 1, 2023

Language: Английский

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