Nickel-Catalyzed Dicarbofunctionalization of Alkenes

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(15), P. 8542 - 8556

Published: July 2, 2020

1,2-Dicarbofunctionalization of alkenes has emerged as an efficient synthetic strategy for preparing substituted molecules by coupling readily available with electrophiles and/or nucleophiles. Nickel complexes serve effective catalysts owing to their tendency undergo facile oxidative addition and slow β-hydride elimination, capability access both two-electron radical pathways. Two-component alkene functionalization reactions have achieved high chemo-, regio-, stereoselectivities tethering one the partners substrate. Three-component reactions, however, often incorporate directing groups control selectivity. Only a few examples directing-group-free difunctionalizations unactivated been reported. Therefore, great opportunities exist development three-component difunctionalization broad substrate scopes tunable stereoselectivities.

Language: Английский

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Nickel-Catalyzed Enantioconvergent Reductive Hydroalkylation of Olefins with α-Heteroatom Phosphorus or Sulfur Alkyl Electrophiles

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 142(1), P. 214 - 221

Published: Dec. 15, 2019

Substantial advances in enantioconvergent C(sp3)–C(sp3) bond formation reactions have been made recent years through the use of transition-metal-catalyzed cross-coupling racemic secondary alkyl electrophiles with organometallic reagents. Herein, we report a general process for asymmetric construction alkyl–alkyl bonds adjacent to heteroatoms, namely, nickel-catalyzed reductive hydroalkylation olefins α-heteroatom phosphorus or sulfur electrophiles. Including readily available olefins, this reaction has considerable advantages, such as mild conditions, broad substrate scope, and good functional group compatibility, making it desirable alternative traditional electrophile–nucleophile reactions.

Language: Английский

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Enantioselective C(sp3)–C(sp3) cross-coupling of non-activated alkyl electrophiles via nickel hydride catalysis

Nature Chemistry, Journal Year: 2020, Volume and Issue: 13(3), P. 270 - 277

Published: Dec. 30, 2020

Language: Английский

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Recent advances in nickel-catalyzed reductive hydroalkylation and hydroarylation of electronically unbiased alkenes

Science China Chemistry, Journal Year: 2020, Volume and Issue: 63(11), P. 1586 - 1600

Published: Sept. 28, 2020

Language: Английский

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Chiral Alkyl Amine Synthesis via Catalytic Enantioselective Hydroalkylation of Enecarbamates

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(4), P. 1959 - 1967

Published: Jan. 22, 2021

Chiral alkyl amines are omnipresent as bioactive molecules and synthetic intermediates. The catalytic enantioselective synthesis of from readily accessible precursors is challenging. Here we develop a nickel-catalyzed hydroalkylation method to assemble wide range chiral enecarbamates (N-Cbz-protected enamines) halides with high regio- enantioselectivity. works for both nonactivated activated able produce enantiomerically enriched two minimally differentiated α-alkyl substituents. mild conditions lead functional group tolerance, which demonstrated in the postproduct functionalization many natural products drug molecules, well building blocks key intermediates compounds.

Language: Английский

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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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NiH-catalyzed asymmetric hydroarylation of N-acyl enamines to chiral benzylamines

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

Published: Jan. 27, 2021

Enantiomerically pure chiral amines and related amide derivatives are privilege motifs in many pharmacologically active molecules. In comparison to the well-established hydroamination, transition metal-catalysed asymmetric hydrofunctionalization of enamines provides a complementary approach for their construction. Here we report NiH-catalysed enantio- regioselective reductive hydroarylation N-acyl enamines, allowing practical access broad range structurally diverse, enantioenriched benzylamines under mild, operationally simple reaction conditions.

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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