Enantioselective C(sp³)–C(sp³) Reductive Cross-Electrophile Coupling of Unactivated Alkyl Halides with α-Chloroboronates via Dual Nickel/Photoredox Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(4), С. 2081 - 2087

Опубликована: Янв. 23, 2023

Substantial advances in enantioconvergent C(sp3)-C(sp3) bond formations have been made with nickel-catalyzed cross-coupling of racemic alkyl electrophiles organometallic reagents or nickel-hydride-catalyzed hydrocarbonation alkenes. Herein, we report an unprecedented enantioselective reductive by the direct utilization two different halides dual nickel/photoredox catalysis system. This highly selective coupling α-chloroboronates and unactivated iodides furnishes chiral secondary boronic esters, which serve as useful important intermediates realm organic synthesis enable a desirable protocol to fast construction enantioenriched complex molecules.

Язык: Английский

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Diborodichloromethane as Versatile Reagent for Chemodivergent Synthesis of gem‐Diborylalkanes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(3)

Опубликована: Дек. 8, 2023

Abstract The development of boron reagents is crucial for synthetic chemistry. Herein, we present a scalable and practical synthesis diborodichloromethane (DBDCM) through the reaction trichloromethyllithium with bis(pinacolato)diboron (B 2 pin ). resulting DBDCM reagent serves as basic unit construction various structurally diverse gem ‐diborylalkanes controllable C−Cl functionalizations. Moreover, have developed consecutive tetra‐functionalizations tertiary quaternary carbon containing molecules. use isotopically enriched 13 C‐chloroform 10 B enables C‐DBDCM B‐DBDCM reagents, which are beneficial convenient carbon‐13 boron‐10

Язык: Английский

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Direct Light‐Enabled Access to α‐Boryl Radicals: Application in the Stereodivergent Synthesis of Allyl Boronic Esters**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(34)

Опубликована: Июнь 16, 2023

Abstract Operationally simple strategies to assemble boron containing organic frameworks are highly enabling in synthesis. While conventional retrosynthetic logic has engendered many platforms focusing on the direct formation of C−B bonds, α‐boryl radicals have recently reemerged as versatile open‐shell alternatives access organoborons via adjacent C−C bond formation. Direct light‐enabled α‐activation is currently contingent photo‐ or transition metal‐catalysis activation efficiently generate radical species. Here, we disclose a facile α‐halo boronic esters using only visible light and Lewis base enable homolytic scission. Intermolecular addition styrenes facilitates rapid construction E ‐allylic esters. The simplicity permits strategic merger this construct with selective energy transfer catalysis complimentary stereodivergent synthesis Z

Язык: Английский

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Modular Access tometa-Substituted Benzenes via Mo-Catalyzed Intermolecular Deoxygenative Benzene Formation

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(16), С. 8781 - 8787

Опубликована: Март 17, 2023

The substituted benzene derivatives are essential to organic synthesis, medicinal chemistry, and material science. However, the 1,3-di- 1,3,5-trisubstituted benzenes far less prevalent in small-molecule drugs than other substitution patterns, likely due lack of robust, efficient, convenient synthetic methods. Here, we report a Mo-catalyzed intermolecular deoxygenative benzene-forming reaction readily available ynones allylic amines. A wide range unsymmetric unfunctionalized were obtained up 88% yield by using commercially molybdenum catalyst. potential method was further illustrated transformations, scale-up derivatization bioactive molecules. Preliminary mechanistic studies suggested that this process might proceed through aza-Michael addition/[1,5]-hydride shift/cyclization/aromatization cascade. This strategy not only provided facile, modular approach various meta-substituted but also demonstrated catalysis challenging cross-coupling reactions.

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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The current utility and future potential of multiborylated alkanes

Nature Reviews Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Сен. 26, 2024

Язык: Английский

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Mechanochemical Synthesis of α‐halo Alkylboronic Esters

Advanced Science, Год журнала: 2024, Номер 11(33)

Опубликована: Июль 3, 2024

α-halo alkylboronic esters, acting as ambiphilic synthons, play a pivotal role versatile intermediates in fields like pharmaceutical science and organic chemistry. The sequential transformation of carbon-boron carbon-halogen bonds into broad range carbon-X allows for programmable bond formation, facilitating the incorporation multiple substituents at single position streamlining synthesis complex molecules. Nevertheless, synthetic potential these compounds is constrained by limited reaction patterns. Additionally, conventional methods often necessitate use bulk toxic solvents, exhibit sensitivity to air/moisture, rely on expensive metal catalysts, involve extended times. In this report, ball milling technique introduced that overcomes limitations, enabling external catalyst-free multicomponent coupling aryl diazonium salts, alkenes, simple halides. This approach offers general straightforward method obtaining diverse array thereby paving way extensive utilization synthons fine chemicals.

Язык: Английский

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Stereospecific C–O sulfation via persulfate-induced 1,4-metallate migration

Nature Synthesis, Год журнала: 2024, Номер unknown

Опубликована: Сен. 5, 2024

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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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Catalytic Intermolecular Deoxygenative Coupling of Carbonyl Compounds with Alkynes by a Cp*Mo(II)-Catalyst

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5605 - 5613

Опубликована: Фев. 14, 2024

Carbonyl is highly accessible and acts as an essential functional group in chemical synthesis. However, the direct catalytic deoxygenative functionalization of carbonyl compounds via a putative metal carbene intermediate formidable challenge due to requirement high activation energy for cleavage strong C═O double bonds. Here, we report class bench stable readily available Cp*Mo(II)-complexes efficient deoxygenation catalysts that could catalyze intermolecular coupling with alkynes. Enabled by this powerful Cp*Mo(II)-catalyst, various valuable heteroarenes (10 different classes) were obtained generally good yields remarkable chemo- regioselectivities. Mechanistic studies suggested reaction might proceed sequence bonds cleavage, carbene-alkyne metathesis, cyclization, aromatization processes. This strategy not only provided general platform rapid preparation but also opened new window applications Cp*Mo(II)-catalysts organic

Язык: Английский

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