Cobalt‐Catalyzed Enantioselective Alkenylation of Aldehydes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)

Published: May 31, 2024

Catalytic enantioselective alkenylation of aldehydes with easily accessible alkenyl halides promoted by a chiral cobalt complex derived from newly developed tridentate bisoxazolinephosphine is presented. Such processes represent an unprecedented reaction pathway for catalysis and general approach that enable rapid construction highly diversified enantioenriched allylic alcohols containing 1,1-, 1,2-disubstituted trisubstituted alkene as well axial stereogenicity in up to 99 % yield : 1 er without the need preformation alkenyl-metal reagents. DFT calculations revealed origin enantioselectivity.

Language: Английский

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Visible Light‐Mediated Cobalt and Photoredox Dual‐Catalyzed Asymmetric Reductive Coupling for Axially Chiral Secondary Alcohols^†

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(23), P. 3253 - 3260

Published: July 20, 2023

Comprehensive Summary Secondary alcohols bearing both axial and central chirality comprise attractive biological activity exhibit excellent chiral induction in asymmetric reactions. However, only very limited catalytic approaches were developed for their synthesis. We herein describe visible light‐mediated cobalt‐catalyzed reductive Grignard‐type addition of aryl iodides with axially prochiral biaryl dialdehydes leading to the direct construction secondary alcohols. Preliminary mechanistic studies indicate that efficient kinetic recognition diastereomers might occur improve stereoselectivity, which open a new avenue challenging cascade multiple elements. This protocol features enantio‐ diastereoselectivity, green mild conditions, simple operation, broad substrate scope, providing modular platform synthesis

Language: Английский

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Pathway-divergent coupling of 1,3-enynes with acrylates through cascade cobalt catalysis

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: April 23, 2024

Catalytic cascade transformations of simple starting materials into highly functionalized molecules bearing a stereochemically defined multisubstituted alkene, which are important in medicinal chemistry, natural product synthesis, and material science, high demand for organic synthesis. The development multiple reaction pathways accurately controlled by catalysts derived from different ligands is critical goal the field catalysis. Here we report cobalt-catalyzed strategy direct coupling inexpensive 1,3-enynes with two acrylates to construct diversity 1,3-dienes containing trisubstituted or tetrasubstituted olefin. Such reactions can proceed through three initiated oxidative cyclization achieve bond formation chemo-, regio- stereoselectivity precisely ligands, providing platform tandem carbon-carbon bond-forming reactions.

Language: Английский

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Hydrogen Source Tuned Regiodivergent Asymmetric Hydroalkylations of 2‐Substituted 1,3‐Dienes with Aldehydes by Cobalt‐Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: April 3, 2024

Abstract Catalytic methods allowing for the reliable prediction and control of diverse regioselectivity along with enantioselectivity to access different regio‐ enantiomers by switching least reaction parameters are one most attractive ways in organic synthesis, which provide enantioenriched architectures from identical starting materials. Herein, a Co‐catalyzed regiodivergent enantioselective reductive hydroalkylation 1,3‐dienes aldehydes has been achieved, furnishing homoallylic alcohol good levels enantioselectivity. The features switch tuned selection proton source. use an acid as source provided asymmetric 1,2‐hydroalkylation products under conditions, yet 4,3‐hydroalkylation were obtained silane hydride This catalytic protocol allows alcohols two continuous saturated carbon centers regio‐, diastereo‐,

Language: Английский

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Organocatalytic asymmetric cascade bicyclization: access to chiral polycyclic bisindoles from 2-indolylmethanols and propargylic alcohols

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(7), P. 2040 - 2046

Published: Jan. 1, 2024

A chiral phosphoric acid-catalyzed asymmetric bis-cyclization of α-indolyl propargylic alcohols with 2-indolylmethanols was realized.

Language: Английский

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Chromium‐ and Metal‐Reductant‐Free Asymmetric Nozaki–Hiyama–Kishi (NHK) Reaction Enabled by Metallaphotoredox Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(37)

Published: June 25, 2024

Abstract Chiral allylic alcohols are highly prized in synthetic chemistry due to their versatile reactivity stemming from both alkenyl and hydroxyl functionalities. While the Nozaki–Hiyama–Kishi (NHK) reaction is a widely used method for synthesis of alcohols, it suffers drawbacks such as use toxic chromium salts, high amounts metal reductants, poor enantiocontrol. To address these limitations, we present novel approach involving metallaphotoredox‐catalyzed asymmetric NHK production chiral alcohols. This marries (pseudo)halides with aldehydes, leveraging synergistic blend nickel catalyst photocatalyst. innovative technique enables oxidative addition insertion just using nickel, diverging significantly conventional pathway mediated by salts. The adoption this methodology holds immense promise crafting spectrum intricate compounds, particularly those significance pharmaceuticals. Detailed experimental investigations have shed light on metallaphotoredox process, further enhancing our understanding enabling advancements.

Language: Английский

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Discovering organic reactions with a machine-learning-powered deciphering of tera-scale mass spectrometry data

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 16, 2025

The accumulation of large datasets by the scientific community has surpassed capacity traditional processing methods, underscoring critical need for innovative and efficient algorithms capable navigating through extensive existing experimental data. Addressing this challenge, our study introduces a machine learning (ML)-powered search engine specifically tailored analyzing tera-scale high-resolution mass spectrometry (HRMS) This harnesses novel isotope-distribution-centric algorithm augmented two synergistic ML models, assisting with discovery hitherto unknown chemical reactions. methodology enables rigorous investigation data, thus providing support hypotheses while reducing conducting additional experiments. Moreover, we extend approach baseline methods automated reaction hypothesis generation. In its practical validation, successfully identified several reactions, unveiling previously undescribed transformations. Among these, heterocycle-vinyl coupling process within Mizoroki-Heck stands out, highlighting capability to elucidate complex phenomena. Mass generates vast amounts data in chemistry labs. Here, authors developed learning-driven that analyzes archived discover reactions without performing

Language: Английский

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A General Enantioselective α-Alkyl Amino Acid Derivatives Synthesis Enabled by Cobalt-Catalyzed Reductive Addition

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

Published: Sept. 12, 2024

Enantioenriched unnatural amino acids represent a prevalent motif in organic chemistry, with profound applications biochemistry, medicinal and materials science. Herein, we report cobalt-catalyzed aza-Barbier reaction of dehydroglycines unactivated alkyl halides to afford α-amino esters high enantioselectivity. This catalytic reductive alkylative addition protocol circumvents the use moisture-, air-sensitive organometallic reagents, stoichiometric chiral auxiliaries, enabling conversion variety primary, secondary, even tertiary α-alkyl-amino under mild conditions, thus leading broad functional group tolerance. The expedient access biologically active motifs demonstrates practicality this by reducing number synthetic steps enhancing efficiency.

Language: Английский

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Radical‐Based Enantioconvergent Reductive Couplings of Racemic Allenes and Aldehydes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 2, 2024

Abstract Transition metal‐catalyzed radical‐based enantioconvergent reactions have become a powerful strategy to synthesize enantiopure compounds from racemic starting materials. However, existing methods primarily address precursors with central chirality, neglecting those axial chirality. Herein, we describe the reductive coupling of allenes aldehydes, facilitated by photoredox, chromium, and cobalt triple catalysis system. This method selectively affords one product sixteen possible regio‐ stereoisomers. The protocol leverages Co III −H mediated hydrogen atom transfer (MHAT) Cr‐catalyzed radical‐polar crossover for efficient stereoablation chirality asymmetric addition, respectively. Supported mechanistic insights control experiments, deuterium labeling, DFT calculations, our approach offers synthetic chemists valuable tool creating enantioenriched chiral homoallylic alcohols, promising advance strategies synthesizing complex molecules.

Language: Английский

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COAP/Pd-catalyzed asymmetric linear allylic alkylation for synthesizing chiral 3,3′-disubstituted oxindoles bearing all-carbon quaternary stereocenters and primary allylic alcohol structures

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(18), P. 5196 - 5201

Published: Jan. 1, 2024

A linear asymmetric allylic alkylation of vinyloxirane catalyzed by a chiral oxalamide–phosphine (COAP)/Pd(0) complex was reported. Various 3,3′-oxindole derivatives were achieved in good yields with excellent regio- and enantioselectivity.

Language: Английский

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