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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Enantioselective Reductive Cross-Couplings of Olefins by Merging Electrochemistry with Nickel Catalysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(44), P. 23910 - 23917

Published: Oct. 26, 2023

The merger of electrochemistry and transition metal catalysis has emerged as a powerful tool to join two electrophiles in an enantioselective manner. However, the development electroreductive cross-couplings olefins remains challenge. Inspired by advantages synergistic use with nickel catalysis, we present here Ni-catalyzed cross-coupling acrylates aryl halides alkyl bromides, which affords chiral α-aryl carbonyls good excellent enantioselectivity. Additionally, this catalytic reaction can be applied (hetero)aryl chlorides, is difficult achieve other methods. combination cyclic voltammetry analysis electrode potential studies suggests that NiI species activates oxidative addition bromides single-electron transfer.

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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Electrochemical NiH‐Catalyzed C(sp³)−C(sp³) Coupling of Alkyl Halides and Alkyl Alkenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 14, 2023

Herein, an electrochemically driven NiH-catalyzed reductive coupling of alkyl halides and alkenes for the construction Csp3 -Csp3 bonds is firstly reported. Notably, serve dual function as substrates hydrogen sources to generate NiH species under electrochemical conditions. The tunable nature this reaction realized by introducing intramolecular coordinating group substrate, where product can be easily adjusted give desired branched products. method proceeds mild conditions, exhibits a broad substrate scope, affords moderate excellent yields with over 70 examples, including late-stage modification natural products drug derivatives. Mechanistic insights offer evidence process. sp3 -carbon-halogen activated through single electron transfer (SET) nickel catalyst in its low valence state, generated cathodic reduction, generation from pivotal transformation.

Language: Английский

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Photoinduced Selective B–H Activation of nido-Carboranes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7791 - 7802

Published: March 10, 2024

The development of new synthetic methods for B–H bond activation has been an important research area in boron cluster chemistry, which may provide opportunities to broaden the application scope clusters. Herein, we present a reaction strategy direct site-selective functionalization nido-carboranes initiated by photoinduced cage via noncovalent cage···π interaction. As result, nido-carborane radical is generated through single electron transfer from 3D 2D photocatalyst upon irradiation with green light. resulting transient could be directly probed advanced time-resolved EPR technique. In air, subsequent transformations active have led efficient and selective B–N, B–S, B–Se couplings presence N-heterocycles, imines, thioethers, thioamides, selenium ethers. This protocol also facilitates both late-stage modification drugs synthesis nido-carborane-based drug candidates neutron capture therapy (BNCT).

Language: Английский

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Selective 1,4-syn-Addition to Cyclic 1,3-Dienes via Hybrid Palladium Catalysis

ACS Central Science, Journal Year: 2024, Volume and Issue: 10(6), P. 1191 - 1200

Published: May 15, 2024

1,4-cis-Disubstituted cyclic compounds play a pivotal role in pharmaceutical development, offering enhanced potency and bioavailability. However, their stereoselective modular synthesis remains long-standing challenge. Here, we report an innovative strategy for accessing these structures via mild conditions employing 1,3-dienes/alkyl(aryl)halides amines. This procedure exhibits wide substrate scope that tolerates various functional groups. The utility of this method is demonstrated the efficient TRPV6 inhibitor, CFTR modulator, other bioactive molecules. Combined experimental computational studies suggest hybrid palladium-catalyzed radical-polar crossover mechanism crucial achieving exceptional 1,4-syn-addition selectivity (dr > 20:1).

Language: Английский

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Chemo-, regio- and stereoselective access to polysubstituted 1,3-dienes via Nickel-catalyzed four-component reactions

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

Published: June 28, 2024

1,2-Difunctionalization of alkynes offers a straightforward approach to access polysubstituted alkenes. However, simultaneous multi-component cascade transformations including difunctionalization two with both syn- and anti-selectivity in one catalyst system is undeveloped proves be significant challenge. Herein, we report Nickel-catalyzed four-component reaction 1,3-dienes using terminal alkynes, aryl boroxines, perfluoroalkyl iodides, wherein the forms three new C-C bonds single vessel serve as modular strategy excellent chemoselectivity, good regioselectivity exclusive stereoselectivity. Control experiments reveal plausible mechanism DFT calculations explain cause for formation this unusual reaction. Furthermore, successfully incorporate biologically active units into 1,2,3,4-tetrasubstituted 1,3-dienes, which greatly increases diversity molecular scaffolds brings more potential values medicinal chemistry, synthetic utility our protocol further demonstrated by late-stage transformations.

Language: Английский

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Palladium-Catalyzed Site-Selective Regiodivergent Carbocyclization of Di- and Trienallenes: A Switch between Substituted Cyclohexene and Cyclobutene

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 6, 2025

Nature efficiently produces a myriad of structurally diverse carbon ring frameworks from common linear precursors via cyclization reactions at specific olefinic sites in dienes or polyenes. In contrast, achieving the site-selective functionalization diene polyene substrates remains formidable challenge chemical synthesis. Herein, we report pair highly site-selective, regiodivergent carbocyclization dienallenes and trienallenes, enabling efficient synthesis cis-1,4-disubstituted cyclohexenes trans-1,2-disubstituted cyclobutenes precursor with high diastereoselectivity. Remarkably, simple achiral organophosphoric acids amines are identified as powerful ligands for controlling these palladium-catalyzed carbocyclizations. This approach represents first example carbocyclization, providing practical method stereospecific thermodynamically disfavored fully substituted trans-1,2-cyclobutenes. Additionally, methodology developed offers general insights into development metal-catalyzed carbocyclizations precursors, mimicking natural processes.

Language: Английский

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Versatile electrooxidative amino- and oxyselenation of alkenes

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(10), P. 3925 - 3930

Published: Jan. 1, 2023

We herein describe a methodology for the production of organoselenium compounds by electrocatalytic difunctionalisation alkenes.

Language: Английский

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Diastereodivergent and Enantioselective Synthesis of Homoallylic Alcohols via Nickel-Catalyzed Borylative Coupling of 1,3-Dienes with Aldehydes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(35), P. 19195 - 19201

Published: Aug. 24, 2023

We present the first enantioselective nickel-catalyzed borylative coupling of 1,3-dienes with aldehydes, providing an efficient route to highly valuable homoallylic alcohols in a single step. The reaction involves 1,4-carboboration dienes, leading formation C-C and C-B bonds accompanied by construction two continuous stereogenic centers. Enabled chiral spiro phosphine-oxazoline nickel complex, this transformation yields products exceptional diastereoselectivity, E-selectivity, enantioselectivity. diastereoselectivity can be controlled employing either (Z)-1,3-dienes or (E)-1,3-dienes.

Language: Английский

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