NiH-Catalyzed Functionalization of Remote and Proximal Olefins: New Reactions and Innovative Strategies

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(23), P. 3519 - 3536

Published: Nov. 9, 2022

Transition metal hydride catalyzed functionalization of remote and proximal olefins has many advantages over conventional cross-coupling reactions. It avoids the separate, prior generation stoichiometric amounts organometallic reagents use preformed reagents, which are sometimes hard to access may compromise functional group compatibility. The migratory insertion complexes generated in situ into readily available alkene starting materials, hydrometalation process, provides an attractive straightforward route alkyl intermediates, can undergo a variety sequential In particular, with synergistic combination chain-walking chemistry nickel, NiH-catalyzed undergone particularly intense development past few years. This Account aims chronicle progress made this arena terms activation modes, diverse functionalizations, chemo-, regio-, enantioselectivity.We first provide brief introduction general reaction mechanisms. Taking hydroarylation as example, four oxidation states Ni have allowed us develop two different strategies form final product: Ni(I)-H/X-Ni(II)-H platform that relies on reductants Ni(I/II/III) cycle redox-neutral or FG-Ni(II)-H reacts substrate forms products via Ni(0/II) pathway. We also demonstrate functionalization, including C-C bond-forming reactions more challenging C-N/C-S could be realized. Moreover, employment appropriate chiral ligands successfully realize corresponding asymmetric hydrofunctionalization olefins, hydroalkylation, hydroarylation, hydroalkenylation, hydroalkynylation, hydroamination. Interestingly, enantio-determining step enantioselective hydronickelation, selective oxidative addition, reductive elimination. To hydrofunctionalization, we developed ligand relay catalytic strategy simple ligands, for second coupling. novel design single, possibly structurally complex promote both steps success multicomponent convenient approach gain molecules. Finally, halides used olefin precursors cross-electrophile coupling Applications these discussed. hope will inspire future field overcome key challenges, conceptually new strategies, high-performance systems enhanced reactivity selectivity, cutting-edge catalyst design, further mechanistic studies.

Language: Английский

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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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Enantioselective access to chiral aliphatic amines and alcohols via Ni-catalyzed hydroalkylations

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: May 13, 2021

Abstract Chiral aliphatic amine and alcohol derivatives are ubiquitous in pharmaceuticals, pesticides, natural products fine chemicals, yet difficult to access due the challenge differentiate between spatially electronically similar alkyl groups. Herein, we report a nickel-catalyzed enantioselective hydroalkylation of acyl enamines enol esters with halides afford enantioenriched α-branched amines good yields excellent levels enantioselectivity. The operationally simple protocol provides straightforward chiral secondary alkyl-substituted from starting materials great functional group tolerance.

Language: Английский

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Nickel-Catalyzed Multicomponent Coupling: Synthesis of α-Chiral Ketones by Reductive Hydrocarbonylation of Alkenes

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(35), P. 14089 - 14096

Published: Aug. 26, 2021

A nickel-catalyzed, multicomponent regio- and enantioselective coupling via sequential hydroformylation carbonylation from readily available starting materials has been developed. This modular hydrofunctionalization strategy enables the straightforward reductive hydrocarbonylation of a broad range unactivated alkenes to produce wide variety unsymmetrical dialkyl ketones bearing functionalized α-stereocenter, including enantioenriched chiral α-aryl α-amino ketones. It uses bisoxazoline as ligand, silane reductant, chloroformate safe CO source, racemic secondary benzyl chloride or an N-hydroxyphthalimide (NHP) ester protected acid alkylation reagent. The benign nature this process renders method suitable for late-stage functionalization complex molecules.

Language: Английский

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Enantioselective NiH‐Catalyzed Reductive Hydrofunctionalization of Alkenes

Chinese Journal of Chemistry, Journal Year: 2021, Volume and Issue: 40(5), P. 651 - 661

Published: Dec. 3, 2021

Comprehensive Summary Enantioselective NiH‐catalyzed reductive hydrofunctionalization of olefins has attracted much attention in recent years. Using simple chiral ligands, a wide array functionalized and electrophiles can undergo diverse transformations to afford hydrofunctionalized products, regio‐ enantioselectively. These processes avoid the prior preparation organometallic reagents, construct stereogenic center at carbon originating either from olefin or electrophile. This review discusses background, major progress mechanistic investigations this reaction.

Language: Английский

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Thioether-Directed NiH-Catalyzed Remote γ-C(sp³)–H Hydroamidation of Alkenes by 1,4,2-Dioxazol-5-ones

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(37), P. 14962 - 14968

Published: Sept. 8, 2021

A NiH-catalyzed thioether-directed cyclometalation strategy is developed to enable remote methylene C–H bond amidation of unactivated alkenes. Due the preference for five-membered nickelacycle formation, chain-walking isomerization initiated by NiH insertion an alkene can be terminated at γ-methylene site from moiety. By employing 2,9-dibutyl-1,10-phenanthroline (L4) as ligand and dioxazolones reagent, occurs γ-C(sp3)–H bonds afford amide products in up 90% yield (>40 examples) with remarkable regioselectivity (up 24:1 rr).

Language: Английский

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Facile Synthesis of Chiral Arylamines, Alkylamines and Amides by Enantioselective NiH‐Catalyzed Hydroamination

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(44), P. 23584 - 23589

Published: Aug. 27, 2021

Regio- and enantioselective hydroarylamination, hydroalkylamination hydroamidation of styrenes have been developed by NiH catalysis with a simple bioxazoline ligand under mild conditions. A wide range enantioenriched benzylic arylamines, alkylamines amides can be easily accessed nitroarenes, hydroxylamines dioxazolones, respectively as amination reagents. The chiral induction in these reactions is proposed to proceed through an enantiodifferentiating syn-hydronickellation step.

Language: Английский

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Stereodivergent Synthesis of BothZ- andE-Alkenes by Photoinduced, Ni-Catalyzed Enantioselective C(sp³)–H Alkenylation

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(21), P. 13567 - 13574

Published: Oct. 25, 2021

The enantio- and stereoselective synthesis of stereodefined alkenes, especially the functionalized Z-isomer with an allylic stereogenic center, remains a great challenge. We herein report enantioselective benzylic C(sp3)–H alkenylation simple alkylarenes vinyl bromides via photoinduced nickel catalysis, which allows for stereodivergent both enantioenriched Z- E-alkenes bearing aryl-substituted, tertiary centers. Interestingly, tunable Z/E-selectivity is achieved by energy transfer catalysis judicious choice photocatalyst counteranion. This versatile strategy features starting materials, mild reaction conditions, broad substrate scope, divergent E-selectivity, high enantioselectivities. Moreover, formal asymmetric alkylation can also be one-pot alkenylation/reduction sequence, providing complementary to address notoriously challenging stereochemical control in C(sp3)–C(sp3) bond construction.

Language: Английский

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Recent advances in nickel-catalyzed asymmetric hydrofunctionalization of alkenes

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(11), P. 3140 - 3162

Published: Nov. 1, 2022

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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