Asymmetric Carbohydroxylation of Alkenes Using Photoenzymatic Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(31), С. 17018 - 17022

Опубликована: Июль 27, 2023

Alkene difunctionalizations enable the synthesis of structurally elaborated products from simple and ubiquitous starting materials in a single chemical step. Carbohydroxylations olefins represent family reactivity that furnish complex alcohols. While examples this type three-component coupling have been reported, catalytic asymmetric remain elusive. Here, we report an enzyme-catalyzed carbohydroxylation alkenes catalyzed by flavin-dependent "ene"-reductases to produce enantioenriched tertiary Seven rounds protein engineering reshape enzyme's active site increase activity enantioselectivity. Mechanistic studies suggest C–O bond formation occurs via 5-endo-trig cyclization with pendant ketone afford α-oxy radical which is oxidized hydrolyzed form product. This work demonstrates photoenzymatic reactions involving can terminate radicals mechanisms other than hydrogen atom transfer, expanding their utility synthesis.

Язык: Английский

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Kinetic Resolution of Acyclic Tertiary Propargylic Alcohols by NHC-Catalyzed Enantioselective Acylation

Organic Letters, Год журнала: 2024, Номер 26(3), С. 702 - 707

Опубликована: Янв. 11, 2024

We report herein an efficient NHC-catalyzed kinetic resolution of acyclic tertiary propargylic alcohols that provides them in high to excellent enantioselectivity. This is the first example realized by enantioselective acylation. The recovered enantioenriched can be facilely converted into other valuable compounds such as densely functionalized and carbmates yields stereopurity. Density functional theory calculations were performed determine reaction mechanism understand origin enantiodiscrimination.

Язык: Английский

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Pd((R)-DTBM-SEGphos)Cl₂-catalyzed kinetic resolution of tertiary propargylic alcohols

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(9), С. 2477 - 2484

Опубликована: Янв. 1, 2024

A variety of optically active tertiary propargylic alcohols and tetrasubstituted 2,3-allenoic acids have been synthesized via a Pd(( R )-DTBM-SEGphos)Cl 2 -catalyzed carboxylative kinetic resolution reaction racemic alcohols.

Язык: Английский

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Direct enantioselective reduction of C=C bond of β-polyfluoro-alkylated enones via asymmetric photoredox catalysis

Science China Chemistry, Год журнала: 2024, Номер 67(6), С. 2016 - 2021

Опубликована: Март 1, 2024

Язык: Английский

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Stereoselective Synthesis of Axially Chiral Allenes and Styrenes via Chiral Phosphoric Acid Catalysis: An Overview

ACS Omega, Год журнала: 2024, Номер 9(31), С. 33351 - 33364

Опубликована: Июль 26, 2024

Chiral allenes and styrenes are essential components in fields like medicinal chemistry, materials science, organic synthesis. They serve a crucial role as chiral ligands catalysts asymmetric Over the past decade, there has been significant advancement development of practical methods utilizing organocatalytic strategies for synthesis styrenes. It is noteworthy that despite extensive studies on formation styrenes, existing reviews their construction confined to specific organocatalysis, called phosphoric acid catalysis, less documented. This review aims explore different conceptual approaches based electrophilic species involved reaction produce stereoselective providing insights into recent advancements field. Emphasis placed works published since 2017, with detailed discussions mechanisms examples from literature.

Язык: Английский

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Chiral ruthenium complex/Ph ₂ P(2-furyl)–catalyzed asymmetric nucleophilic addition of aryl aldehyde hydrazones to simple ketones

Science Advances, Год журнала: 2025, Номер 11(12)

Опубликована: Март 21, 2025

An efficient synthesis of chiral tertiary alcohols through asymmetric nucleophilic addition reaction aldehyde hydrazones to simple ketones (especially aryl/methyl ketones) has been well established. Aryl aldehydes could be used as latent benzyl carbanion equivalents via reductive polarity reversal. The key the success was combination an achiral monophosphine ligand Ph 2 P(2-furyl) with a diamine derivative, which enhanced enantioselectivity and reactivity. Density functional theory calculations revealed hydrogen bond interactions between ligand, base anion, combined induce desired enantioselectivity. Moreover, further synthetic transformation high chirality transfer also demonstrated.

Язык: Английский

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Electrochemical Strategy for the Radical Fluoroacetylation of Sulfoximines from Fluorinated Alkyl Carboxylic Acids

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 15, 2025

The integration of trifluoroacetyl (CF3CO) groups into organic skeletons is a key research topic in synthetic chemistry given their significant potential to boost biological activity. Despite recent developments strategies for incorporating moiety via radical intermediates, the practical utilization inexpensive and readily available trifluoroacetic acids as sources has not yet been developed. Herein, an electrochemical strategy employed achieve deoxygenative transformation directly with assistance PPh3. obtained radicals are then coupled sulfoximine species, thus enabling synthesis N-trifluoroacetylated sulfoximines. Additionally, other fluorinated alkyl carboxylic acids, including perfluoro-, difluoro-, trifluoromethylcarboxylic can also be efficiently utilized under these conditions, leading corresponding acylated Moreover, trifluoroacetylation drug-based molecules easy execution scale-up experiments highlight applicability this protocol.

Язык: Английский

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A Pd-catalyzed highly selective three-component protocol for trisubstituted allenes

Chemical Science, Год журнала: 2023, Номер 14(28), С. 7709 - 7715

Опубликована: Янв. 1, 2023

A novel three-component protocol to synthesize trisubstituted allenes from 2-alkynyl-1,4-diol dicarbonate with organoboronic acid and malonate has been developed.

Язык: Английский

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Rh-Catalyzed Carbonylative Cyclization of Propargylic Alcohols with Aryl Boronic Acids

Organic Letters, Год журнала: 2024, Номер 26(29), С. 6279 - 6283

Опубликована: Июль 18, 2024

2(3

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Ph₃P═O-Catalyzed Reductive Deoxygenation of Alcohols

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(21), С. 16022 - 16027

Опубликована: Окт. 11, 2024

Reductive deoxygenation of alcohols is particularly challenging because the high bond dissociation energy C–OH and poor leaving ability hydroxyl group. Herein we describe a Ph3P═O-catalyzed reductive benzyl with PhSiH3 under an air atmosphere within 30 min reaction time. The use catalytic loading Ph3P═O enhances practicality this protocol.

Язык: Английский

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