Deoxygenative Haloboration and Enantioselective Chloroboration of Carbonyls

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(50), С. 22870 - 22876

Опубликована: Дек. 7, 2022

Deoxygenative difunctionalization of carbonyls affords a straightforward and effective route to construct geminal dual functionalized motifs. However, the research in this field is very challenging due strong bond dissociation energies C–O double or subsequently formed bond. Herein, we report highly efficient deoxygenative haloboration aldehydes generate secondary α-haloboronates. Meanwhile, difficult-to-obtain tertiary α-haloboronates can be also readily prepared via same strategy with ketones. Furthermore, enantioselective chloroboration was successfully achieved give chiral α-chloroboronates, important intermediates access enantioenrich multisubstituted stereocenters. These versatile products surprisingly attained through simple mild process remarkable substrate scope expansion functional group tolerance. Additionally, these reactions proceed well on large scales, giving more practical values application.

Язык: Английский

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Updated Progress of the Copper-Catalyzed Borylative Functionalization of Unsaturated Molecules

Molecules, Год журнала: 2023, Номер 28(5), С. 2252 - 2252

Опубликована: Фев. 28, 2023

Borylation has become a powerful method to synthesize organoboranes as versatile building blocks in organic synthesis, medicinal chemistry, and materials science. Copper-promoted borylation reactions are extremely attractive due the low cost non-toxicity of copper catalyst, mild reaction conditions, good functional group tolerance, convenience chiral induction. In this review, we mainly updated recent advances (from 2020 2022) synthetic transformations C=C/C≡C multiple bonds, C=E bonds mediated by boryl systems.

Язык: Английский

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Selectively Tunable Synthesis of α-Trifluoromethyl Ketones

Organic Letters, Год журнала: 2023, Номер 25(13), С. 2344 - 2348

Опубликована: Март 23, 2023

A cross-coupling of aldehydes and α-trifluoromethyl alkyl bromides was developed via dual nickel/photoredox catalysis system. wide variety substrates bearing a diverse set functional groups were compatible to afford ketones under very mild conditions (visible light, ambient temperature, no strong base). Selectively tunable access these with the trifluoromethyl group on any one side can be smoothly obtained by simply modulating different reagents. Meanwhile, asymmetric pattern also investigated.

Язык: Английский

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Enantioconvergent Reductive C(sp)−C(sp³) Cross‐Coupling to Access Chiral α‐Alkynyl Phosphonates Under Dual Nickel/Photoredox Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(18)

Опубликована: Март 8, 2023

Transition-metal-catalyzed asymmetric carbon-carbon bond formation to forge phosphonates with an α-chiral carbon center through C(sp3 )-C(sp3 ) and C(sp2 couplings has been successful. However, the enantioselective C(sp)-C(sp3 coupling not yet disclosed. Reported herein is unprecedented enantioconvergent cross-coupling of alkynyl bromides α-bromo deliver chiral α-alkynyl phosphonates.

Язык: Английский

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Dual Nickel- and Photoredox-Catalyzed Asymmetric Reductive Cross-Couplings: Just a Change of the Reduction System?

Accounts of Chemical Research, Год журнала: 2024, Номер 57(14), С. 1997 - 2011

Опубликована: Июль 4, 2024

ConspectusIn recent years, nickel-catalyzed asymmetric coupling reactions have emerged as efficient methods for constructing chiral C(sp

Язык: Английский

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Synthesis of substituted benzylboronates by light promoted homologation of boronic acids with N-sulfonylhydrazones

Chemical Science, Год журнала: 2023, Номер 14(47), С. 13765 - 13775

Опубликована: Янв. 1, 2023

The homologation of boronic acids with diazoalkanes obtained by photochemical decomposition N -tosylhydrazones leads to substituted benzylboronates, previously unavailable under thermal conditions. Batch and continuous flow reactions are described.

Язык: Английский

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Stereoselective Construction of Multifunctional C-Glycosides Enabled by Nickel-Catalyzed Tandem Borylation/Glycosylation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(32), С. 22413 - 22423

Опубликована: Авг. 3, 2024

Stereochemically pure saccharides have indispensable roles in fields ranging from medicinal chemistry to materials science and organic synthesis. However, the development of a simple, stereoselective, efficient glycosylation protocol access α- β-C-glycosides (particularly 2-deoxy entities) remains persistent challenge. Existing studies primarily focused on C1 modification carbohydrates transformation glycosyl radical precursors. Here, we innovate by harnessing situ generated glycosyl-Ni species achieve one-pot borylation cascade manner, which is enabled an earth-abundant nickel-catalyzed carboboration readily accessible glycals without any ligand. This work reveals potential for modular multifunctional platform facilitate simultaneous introduction C-C C-B bonds at stereogenic center saccharides, largely unexploited research area. Preliminary experimental computational indicate that endocyclic O C3 group play important stereoseclectively forging glycosidic bonds. As result, diverse range C-R (R = alkyl, aryl, alkenyl) 2-deoxygenated glycosides bearing modifiable boron groups could be rapidly made with excellent stereocontrol exhibit remarkable functional tolerance. The synthetic underscored late-stage natural products commercial drugs as well facile preparation various rare sugars, bioactive conjugates, key intermediates prorocentin, phomonol, aspergillide A.

Язык: Английский

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Visible-light-mediated deoxygenative transformation of 1,2-dicarbonyl compounds through energy transfer process

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Окт. 25, 2024

Язык: Английский

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Direct Synthesis of β-Amino Boronates via Amide α-C–H Bond Activation and C(sp³)–C(sp³) Coupling under Dual Ni/Photoredox Catalysis

ACS Catalysis, Год журнала: 2023, Номер 14(1), С. 547 - 553

Опубликована: Дек. 26, 2023

Direct transformations of readily available amines or amides via C–H bond functionalization could provide a fast route for accessing complex molecules. While various groups have been successfully incorporated into the α position nitrogen atom with photoredox system activation, couplings functionalized alkyl halides are still very challenging. Herein, we report direct and convenient protocol β-amino boronates through C(sp3)–C(sp3) coupling α-bromoboronates. The mild conditions allow good functional group tolerance broad scope. application method in late-stage modification molecules further demonstrates its great potential organic synthesis. Mechanistic studies were also conducted, catalytic cycle is proposed.

Язык: Английский

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Electrochemical Deoxyarylation of Aromatic Aldehydes and Ketones

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 10, 2025

Carbonyl-containing compounds serve as essential building blocks in various synthetic processes. However, due to the high bond energy of C═O double bond, traditional deoxygenation methods often require harsh conditions or toxic reagents. Direct carbonyl deoxygenative coupling aldehydes and ketones is still challenging under mild conditions. Herein we report successful establishment an electroreductive strategy utilizing aromatic carbonyls terephthalonitrile. A key component our approach use closo-boranes, specifically (Et4N)2B10H10, which situ deoxidant by single-electron oxidation.

Язык: Английский

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