Cu-Catalyzed Asymmetric Dicarboxylation of 1,3-Dienes with CO₂

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 2919 - 2927

Published: Jan. 26, 2024

Dicarboxylic acids and derivatives are important building blocks in organic synthesis, biochemistry, the polymer industry. Although catalytic dicarboxylation with CO2 represents a straightforward sustainable route to dicarboxylic acids, it is still highly challenging limited generation of achiral or racemic acids. To date, asymmetric give chiral has not been reported. Herein, we report first 1,3-dienes via Cu catalysis. This strategy provides an efficient environmentally benign high regio-, chemo-, enantioselectivities. The copper self-relay catalysis, that is, Cu-catalyzed boracarboxylation carboxylated allyl boronic ester intermediates subsequent carboxylation C–B bonds dicarboxylates, key success this dicarboxylation. Moreover, protocol exhibits broad substrate scope, good functional group tolerance, easy product derivatizations, facile synthesis liquid crystalline polyester drug-like scaffolds.

Language: Английский

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Catalytic Regio- and Enantioselective Boracarboxylation of Arylalkenes with CO₂ and Diboron

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 2888 - 2894

Published: Jan. 26, 2024

Catalytic asymmetric carboxylation of readily available alkenes with CO2, an abundant and sustainable one-carbon building block, that gives access to value-added α-stereogenic carboxylic acids in atom- step-economic manner is highly attractive. However, it has remained a formidable challenge for the synthetic community. Here, first example Cu-catalyzed regio- enantioselective boracarboxylation reaction on various arylalkenes diboron under atmospheric pressure CO2 described, which afforded variety chiral β-boron-functionalized α-aryl up 87% yield 97% ee mild conditions. Importantly, α-substituted could also be subject this protocol excellent enantiopurities, thereby rendering efficient approach generation enantioenriched α-chiral all-carbon quaternary center. Moreover, high functional group tolerance, scalable synthesis, facile bioactive compounds, like (−)-scopolamine, (−)-anisodamine, (−)-tropicamide, further demonstrated utility strategy.

Language: Английский

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Nickel-Catalyzed Regio- and Enantioselective Borylative Coupling of Terminal Alkenes with Alkyl Halides Enabled by an Anionic Bisoxazoline Ligand

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(25), P. 13603 - 13614

Published: June 6, 2023

Chiral boronic esters are a class of versatile building blocks. We describe herein an asymmetric nickel-catalyzed borylative coupling terminal alkenes with nonactivated alkyl halides. The success this reaction is ascribed to the application chiral anionic bisoxazoline ligand. This study provides three-component strategy access α- and β-stereogenic from easily accessible starting materials. protocol characterized by mild conditions, wide substrate scope high regio- enantioselectivity. also showcase value method in simplifying synthesis several drug molecules. Mechanistic studies suggest that generation enantioenriched bearing α-stereogenic center results stereoconvergent process, while enantioselectivity-controlling step β-stereocenter switched olefin migratory insertion due coordination ester group.

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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Nickel‐Catalyzed Enantioconvergent Carboxylation Enabled by a Chiral 2,2′‐Bipyridine Ligand

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(51)

Published: Oct. 27, 2022

In contrast to previous approaches chiral α-aryl carboxylic acids that based on reactions using hazardous gases, pressurized setup and mostly noble metal catalysts, in this work, a nickel-catalyzed general, efficient highly enantioselective carboxylation reaction of racemic benzylic (pseudo)halides under mild conditions atmospheric CO2 has been developed. A unique 2,2'-bipyridine ligand named Me-SBpy featuring compact polycyclic skeleton enabled both high reactivity stereoselectivity. The utility method demonstrated by synthesis various (30 examples, up 95 % yield 99 : 1 er), including profen family anti-inflammatory drugs transformations the as key intermediates. Based mechanistic experimental results, plausible catalytic cycle involving Ni-complex/radical equilibrium Lewis acid-assisted activation proposed.

Language: Английский

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Palladium-catalyzed regiodivergent hydrochlorocarbonylation of alkenes for formation of acid chlorides

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 31, 2023

Novel strategy for acid chlorides formation that do not use carboxylic acids is particularly attractive in chemical synthesis but remains challenging. Herein, we reported the development of a highly effective Pd-catalyzed hydrochlorocarbonylation alkenes with CO alkyl chlorides. Chlorosilane and AcOH were found as mild HCl source reaction. The reaction shows broad substrate scope produces both branched linear good to high yields upon different ligands solvents. Cooperating follow-up acylation reactions, offers complementary platform diverse carbonyl compounds from alkenes. Mechanistic investigations suggested proceeded though palladium hydride pathway, prompted reductive elimination acyl-Pd-Cl intermediate.

Language: Английский

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Synthesis of Chiral Polycyclic Indoles via Pd(II)-Catalyzed Sequential Cyclization and Carbonylation

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8739 - 8747

Published: May 21, 2024

Asymmetric tandem Heck and carbonylation reactions provide an efficient route to synthesize biologically important chiral cyclic compounds with a carbonyl group have attracted increasing research interests. However, this type of reaction relies on the initiation from oxidative addition aryl halides or pseudo halides, resulting in low atomic economy reaction. In addition, protocol has not adequately demonstrated reactivity generality heteroarene halides. Meanwhile, asymmetric Wacker-type cyclization are plagued by narrow substrate scope enantioselectivity remain underexplored. Herein, we describe Pd(II)-catalyzed sequential 1,6-enynes analogues carbon monoxide (CO). This catalytic system tolerates broad nucleophiles, including phenols, alcohols, amines. sequence forms four chemical bonds, two rings, up three stereocenters single step. strategy allows for convenient access variety polycyclic good yields enantio- diastereoselectivities, indoles, benzofurans, indole- benzofuran-fused bicyclo[3.2.1]octanes, indole-fused bicyclo[4.2.1]nonane.

Language: Английский

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Enantioconvergent synthesis of axially chiral amides enabled by Pd-catalyzed dynamic kinetic asymmetric aminocarbonylation

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

Published: Aug. 23, 2024

Atropisomeric biaryls bearing carbonyl groups have attracted increasing attention due to their prevalence in diverse bioactive molecules and crucial role as efficient organo-catalysts or ligands asymmetric transformations. However, preparation often involves tedious multiple steps, the direct synthesis via carbonylation has scarcely been investigated. Herein, we report an palladium-catalyzed enantioconvergent aminocarbonylation of racemic heterobiaryl triflates with amines dynamic kinetic transformation (DyKAT). This protocol features a broad substrate scope excellent compatibility for rapid construction axially chiral amides good high yields enantioselectivities. Detailed mechanistic investigations discover that base can impede intramolecular hydrogen bond-assisted axis rotation products, thus allowing success achieve enantioselectivity. Moreover, achieved be directly utilized N,N,N-pincer copper-catalyzed enantioselective formation C(sp3)-N C(sp3)-P bonds. Axially containing not only exist various drug candidates but also serve authors transformation.

Language: Английский

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Pd‐Catalyzed Asymmetric 5‐exo‐trig Cyclization/Cyclopropanation/Carbonylation of 1,6‐Enynes for the Construction of Chiral 3‐Azabicyclo[3.1.0]hexanes

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(4)

Published: Nov. 25, 2022

We herein disclose a mild and efficient access to chiral 3-azabicyclo[3.1.0]hexanes via Pd-catalyzed asymmetric 5-exo-trig cyclization/cyclopropanation/carbonylation of 1,6-enynes. Various nucleophiles, such as alcohols, phenols, amines water, are well compatible with the reaction system. This forms three C-C bonds, two rings, adjacent quaternary carbon stereocenters one C-O/C-N bond excellent regio- enantioselectivities. The products could be further functionalized generate library 3-azabicyclo[3.1.0]hexane frameworks.

Language: Английский

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Asymmetric dihydroboration of allenes enabled by ligand relay catalysis

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

Published: Sept. 18, 2024

Language: Английский

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