Diversified Synthesis of Chiral Fluorinated Cyclobutane Derivatives Enabled by Regio‐ and Enantioselective Hydroboration

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 2, 2024

The diversified synthesis of chiral fluorinated cyclobutane derivatives has remained a difficult task in synthetic chemistry. Herein, we present an approach for asymmetric hydroboration and formal hydrodefluorination gem-difluorinated cyclobutenes through rhodium catalysis, providing α-boryl cyclobutanes monofluorinated with excellent regio- enantioselectivity, respectively. key to the success two transformations relies on efficient, mild highly selective rhodium-catalyzed HBPin (pinacolborane), which subsequent addition base, catalytic amount palladium some cases, results formation products four-membered ring retained. obtained are versatile building blocks that provide platform enantioenriched great diversity.

Язык: Английский

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Copper-Catalyzed C–B(sp³) Bond Formation through the Intermediacy of Cu–B(sp³) Complex

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 15, 2025

The vast majority of transition metal (TM) catalyzed borylative transformations rely on TM-B(sp2) complexes. Contrastingly, the chemistry TM-B(sp3) species and their potential in catalytic borylation remain surprisingly underdeveloped, due probably to lack suitable boron(sp3) reagents. Herein, we employ our recently developed sp2-sp3 diboron reagent successfully enable a copper-catalyzed hydroboration allenes for C-B(sp3) bond formation. A comprehensive mechanistic study, including isolation structural characterization Cu-B(sp3) complex, substantiates presence intermediate cycle.

Язык: Английский

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Stereoselective Unsymmetrical 1,1‐Diborylation of Alkynes with a Neutral sp²−sp³ Diboron Reagent

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(48)

Опубликована: Окт. 12, 2023

The incorporation of two distinct boryl groups at the same carbon center in organic molecules has attracted growing research interest due to its potential for facilitating controlled, precise synthesis through stepwise dual carbon-boron bond transformations. Here we report a method access unsymmetrical 1,1-diborylalkene (UDBA) stereoselectively via reaction readily available alkynes with neutral sp2 -sp3 diboron reagent (NHC)BH2 -Bpin (NHC=N-heterocyclic carbene). Attributing chemically easily distinguishable nature and sp3 moieties, controllable derivatization resultant UDBAs is realized. This process leads various multifunctionalized olefins organoborons, such as acylboranes, which are difficult prepare by other methods.

Язык: Английский

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Acridine-based copper(i) PNP pincer complexes: catalysts for alkyne hydroboration and borylation of aryl halides

Dalton Transactions, Год журнала: 2024, Номер 53(10), С. 4471 - 4478

Опубликована: Янв. 1, 2024

Original acridine-based copper( i ) PNP pincer complexes were prepared and their catalytic viability in alkyne hydroboration the borylation of aryl iodides was examined.

Язык: Английский

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Enantioselective Copper-Catalyzed Three-Component Cascade Boronation–Dearomatization Reaction: Synthesis of Chiral Boron-Containing 1,4-Dihydropyridines

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 10, 2025

A three-component cascade boronation–dearomatization reaction of alkenes, a diboron compound, and pyridinium salt is diclosed, affording chiral boron-containing 1,4-dihyropyridines in high yields (≤98%) diastereoselectivity (≤10:1 dr), along with excellent enantioselectivity (typically >99% ee). The catalytic system performs efficiently at low catalyst loadings (1 mol %) was tested >50 examples, including some biologically active molecules.

Язык: Английский

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Enantioselective Synthesis of α‐Hydroxy Allyl Ketones via BINAP‐CuH‐Catalyzed Hydroacylation

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Янв. 31, 2025

Abstract Catalytic hydrocupration of unsaturated carbon‐carbon bonds to generate organometallic nucleophiles has recently become an attractive alternative conventional stoichiometric reagents in the stereoselective synthesis. Herein, we have developed efficient and economical method synthesize enantiopure α ‐hydroxy allyl ketones via a copper hydride (CuH)‐catalyzed hydroacylation alkoxyallenes, significant advancement given scarcity reports on such scaffolds literature. DFT calculations reveal that this reaction proceeds through nucleophilic attack kinetically favourable Z ‐selective allyl‐copper intermediate acid anhydrides six‐membered chair‐like transition state, stabilized by strongly non‐covalent interactions ultimately leads high level enantioselectivities using simple BINAP ligand. This successfully overcomes challenges over‐reduction carbonyl functionality presence CuH‐complex, olefin isomerization highly enolizable ‐stereocenter, which can lead erosion enantioselectivities, making our strategy desirable. The exhibits wide range substrate scope including symmetrical as well carbonic with both aromatic, aliphatic substitutions. In addition, ‐substituted provide exclusive syn α,α′ ‐disubstituted excellent enantiomeric ratios, where allylation occurs one carbonyls containing matched α‐ stereocenter, confirmed mechanistic studies.

Язык: Английский

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Enantioselective Synthesis of α‐Hydroxy Allyl Ketones via BINAP‐CuH‐Catalyzed Hydroacylation

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Янв. 31, 2025

Abstract Catalytic hydrocupration of unsaturated carbon‐carbon bonds to generate organometallic nucleophiles has recently become an attractive alternative conventional stoichiometric reagents in the stereoselective synthesis. Herein, we have developed efficient and economical method synthesize enantiopure α ‐hydroxy allyl ketones via a copper hydride (CuH)‐catalyzed hydroacylation alkoxyallenes, significant advancement given scarcity reports on such scaffolds literature. DFT calculations reveal that this reaction proceeds through nucleophilic attack kinetically favourable Z ‐selective allyl‐copper intermediate acid anhydrides six‐membered chair‐like transition state, stabilized by strongly non‐covalent interactions ultimately leads high level enantioselectivities using simple BINAP ligand. This successfully overcomes challenges over‐reduction carbonyl functionality presence CuH‐complex, olefin isomerization highly enolizable ‐stereocenter, which can lead erosion enantioselectivities, making our strategy desirable. The exhibits wide range substrate scope including symmetrical as well carbonic with both aromatic, aliphatic substitutions. In addition, ‐substituted provide exclusive syn α,α′ ‐disubstituted excellent enantiomeric ratios, where allylation occurs one carbonyls containing matched α‐ stereocenter, confirmed mechanistic studies.

Язык: Английский

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Electrochemical Borylation of C−C and C−Het Bonds

ChemElectroChem, Год журнала: 2025, Номер unknown

Опубликована: Фев. 19, 2025

Abstract Recently, electrochemical methods have been harnessed as a transition metal‐free strategy for borylation reactions in the synthesis of organoboron compounds. This article reviews C−C and C−Het bonds, offering systematic discussion C−C, C−N, C−O, C−S bond reactions. These transformations are applied to substrates including ammonium salts, aryl azo sulfones, carboxylic acids, arylhydrazines, nitroarenes, alcohols, thioethers, showcasing broad compatibility. Additionally, review discusses reaction mechanisms, scalability, practical applications these strategies. The concludes by outlining future research directions reactions, aiming at expending their incorporating boron into wider array organic compounds, challenging unactivated C−F borylations.

Язык: Английский

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Modular Synthesis of Chiral 1,3-Diboronates with Differentiable Boryl Groups via Cu-Catalyzed Borylalkylation of Styrenes

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 8913 - 8924

Опубликована: Май 12, 2025

Язык: Английский

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Asymmetric Radical Oxyboration of β‐Substituted Styrenes via Late‐Stage Stereomutation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(48)

Опубликована: Окт. 11, 2023

Herein, we report an unprecedented copper-catalyzed highly enantio- and diastereoselective radical oxyboration of β-substituted styrenes. The lynchpin success is ascribed to the development a late-stage stereomutation strategy, which enables enantioenriched cis-isomers among couple early-generated diastereomers be converted into trans-isomer counterparts, thus fulfilling high diastereocontrol; while degree enantio-differentiation determined by borocupration process C=C bond. This reaction provides efficient protocol access trans-1,2- dioxygenation products. value this method has further been highlighted in diversity follow-up stereospecific transformations modifying complex molecules.

Язык: Английский

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