Streamlined Alkylation via Nickel-Hydride-Catalyzed Hydrocarbonation of Alkenes

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(16), P. 7015 - 7029

Published: April 12, 2022

Compounds rich in sp3-hybridized carbons are desirable drug discovery. Nickel-catalyzed hydrocarbonation of alkenes is a potentially efficient method to synthesize these compounds. By using abundant, readily available, and stable as pro-nucleophiles, reactions can have broad scope high functional group tolerance. However, this methodology still an early stage development, the first examples were reported only 2016. Herein, we summarize progress emerging field, with emphasis on enantioselective reactions. We highlight major developments, critically discuss wide range possible mechanisms, offer our perspective state challenges field. hope Perspective will stimulate future works area, making widely applicable organic synthesis.

Language: Английский

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Electroreductive Dicarboxylation of Unactivated Skipped Dienes with CO₂

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: April 3, 2023

Carboxylation of easily available alkenes with CO2 is highly important to afford value-added carboxylic acids. Although dicarboxylation activated alkenes, especially 1,3-dienes, has been widely investigated, the challenging unactivated 1,n-dienes (n>3) remains unexplored. Herein, we report first skipped dienes via electrochemistry, affording valuable dicarboxylic Control experiments and DFT calculations support single electron transfer (SET) reduction its radical anion, which followed by sluggish addition SET unstabilized alkyl radicals carbanions nucleophilic attack on give desired products. This reaction features mild conditions, broad substrate scope, facile derivations products promising application in polymer chemistry.

Language: Английский

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Nickel Chain-Walking Catalysis: A Journey to Migratory Carboboration of Alkenes

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(22), P. 3246 - 3259

Published: Nov. 1, 2023

ConspectusChain-walking offers extensive opportunities for innovating synthetic methods that involve constructing chemical bonds at unconventional sites. This approach provides previously inaccessible retrosynthetic disconnections in organic synthesis. Through chain-walking, transition metal-catalyzed alkene difunctionalization reactions can take place a 1,n-addition (n ≠ 2) mode. Unlike classical 1,2-regioselective reactions, there remains scarcity of reports regarding migratory patterns. Moreover, the range olefins utilized these studies is quite limited.About five years ago, our research group embarked on project aimed developing valuable alkenes through chain-walking. Our focus was carboboration utilizing nickel catalysis. The reaction commences with insertion an olefin into Ni-Bpin species. Subsequently, thermodynamically stable alkyl complex generated chain-walking process. then couples carbon-based electrophile, leading to formation alkylboron compound. It worth highlighting success transformations relies significantly utilization bisnitrogen-based ligand and LiOMe as B2pin2 activator. Synthetically, establish robust platform rapid efficient synthesis wide structurally diverse organoboron compounds, which are not facially accessed by conventional methods. incorporation versatile boron introduces wealth possibilities subsequent diversifications, enhancing value resulting products allowing creation broader derivatives applications.This Account comprehensive overview efforts advancements field unactivated using We begin outlining development series 1,1-regioselective terminal alkenes. A significant placed initial integration boronate, only triggers metal species but also exerts control over remote stereochemistry involving substituted methylenecyclohexenes. Continuing exploration, remarkable achieved 1,3-regio- cis-stereoselectivity when dealing cyclic Remarkably, catalysis enables heterocyclic be viable coupling partners within transformations. it grants us ability achieve regioselectivity cyclohexenes unattainable, thus expanding horizons regiochemical reactions. Lastly, we present evolution ligand-modulated regiodivergent allylarenes. By gaining insights underlying mechanisms driving regiodivergence, lay strong foundation tackling challenges related selecting specific sites especially multiple factors. anticipate findings, coupled mechanistic we've gained, will advance realm contribute understanding selectivity this nature. advancement catalyze intricate functional molecules, contributing compounds chemistry.

Language: Английский

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Electroreduction Enables Regioselective 1,2‐Diarylation of Alkenes with Two Electrophiles

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(17)

Published: Feb. 24, 2023

Precisely introducing two similar functional groups into bulk chemical alkenes represents a formidable route to complex molecules. Especially, the selective activation of electrophiles is in crucial demand, yet challenging for cross-electrophile-coupling. Herein, we demonstrate redox-mediated electrolysis, which aryl nitriles are both radical precursors and redox-mediators, enables an intermolecular alkene 1,2-diarylation with remarkable regioselectivity, thereby avoiding involvement transition-metal catalysts. This transformation utilizes cyanoarene anions activating various halides (including iodides, bromides, even chlorides) affords adducts up 83 % yield >20 : 1 regioselectivity more than 80 examples, providing feasible approach bibenzyl derivatives.

Language: Английский

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Nickel-catalysed enantioselective alkene dicarbofunctionalization enabled by photochemical aliphatic C–H bond activation

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(6), P. 655 - 665

Published: April 29, 2024

Abstract The development of novel strategies to rapidly construct complex chiral molecules from readily available feedstocks is a long-term pursuit in the chemistry community. Radical-mediated alkene difunctionalizations represent an excellent platform towards this goal. However, asymmetric versions remain highly challenging, and more importantly, examples featuring simple hydrocarbons as reaction partners are elusive. Here we report three-component dicarbofunctionalization capitalizing on direct activation C( sp 3 )–H bonds through combination photocatalysed hydrogen atom transfer nickel catalysis. This protocol provides efficient for installing two vicinal carbon–carbon across alkenes atom-economic fashion, providing wide array high-value α-aryl/alkenyl carbonyls phosphonates, well 1,1-diarylalkanes ubiquitous alkane, ether alcohol feedstocks. method exhibits operational simplicity, broad substrate scope regioselectivity, chemoselectivity enantioselectivity. compatibility with bioactive motifs expedient synthesis pharmaceutically relevant highlight synthetic potential protocol.

Language: Английский

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Iron-catalyzed fluoroalkylative alkylsulfonylation of alkenes via radical-anion relay

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

Published: Feb. 17, 2024

Abstract Transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides is a powerful method for upgrading commodity chemicals into densely functionalized molecules. However, super stoichiometric amounts metal reductant and the requirement installing directing group to suppress inherent β-H elimination bring great limitations this type reaction. We demonstrate herein that two different accessible via radical-anion relay Na 2 S O 4 as both sulfone-source. The together electron-shuttle catalyst crucial divert mechanistic pathway toward formation sulfone anion instead previously reported alkylmetal intermediates. Mechanistic studies allow identification carbon-centered radical sulfur-centered radical, which are in equilibrium capture or extrusion SO could be converted accelerated by iron catalysis, leading observed high chemoselectivity.

Language: Английский

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Three-component 1,2-dicarbofunctionalization of alkenes involving alkyl radicals

Chemical Communications, Journal Year: 2021, Volume and Issue: 58(6), P. 730 - 746

Published: Dec. 8, 2021

This article provides a comprehensive perspective on three-component 1,2-dicarbofunctionalization of alkenes involving alkyl radicals, which generated from structurally diverse electrophilic and nucleophilic precursors under mild conditions.

Language: Английский

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Nickel‐Catalyzed Switchable Site‐Selective Alkene Hydroalkylation by Temperature Regulation**

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 25, 2022

Regiodivergent alkene functionalization that produces either regioisomer starting from the same raw materials is desirable. Herein, we report a nickel-catalyzed switchable site-selective hydroalkylation. The selection of reaction temperatures leads to protocols provide regiodivergent hydroalkylated products single substrate. This protocol allows convenient synthesis α- and β-branched protected amines, both which are important fields pharmaceutical chemistry biochemistry. In addition, enantioenriched alkylamines can be accessed in catalytic asymmetric variant. Preliminary mechanistic studies indicate formation more stable nickelacycle provides driving force migration. thermodynamic kinetic properties different reduction elimination intermediates responsible for site-selectivity.

Language: Английский

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Photoredox cooperative N-heterocyclic carbene/palladium-catalysed alkylacylation of alkenes

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Sept. 30, 2022

Three-component carboacylation of simple alkenes with readily available reagents is challenging. Transition metal-catalysed intermolecular works for strained ring or directing groups. Herein, we develop a photoredox cooperative N-heterocyclic carbene/Pd-catalysed alkylacylation aldehydes and unactivated alkyl halides to provide ketones in good yields. This multicomponent coupling reaction features wide scope alkenes, broad functional group compatibility free exogenous photosensitizer external reductant. In addition, series chlorinated cyclopropanes one two vicinal quaternary carbons obtained when chloroform carbon tetrachloride used as the halide. The involves radicals from ketyl under carbene/Pd catalysis.

Language: Английский

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Recent advances in transition metal-catalyzed heteroannulative difunctionalization of alkenes via C–H activation for the synthesis of heterocycles

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(8), P. 2256 - 2279

Published: Jan. 1, 2022

In this review article, we summarized recent advances in the transition metal-catalyzed heteroannulative difunctionalization of alkenes via direct C–H activation to access heterocyclic frameworks.

Language: Английский

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