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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Nickel-Catalyzed Remote Asymmetric Hydroalkylation of Alkenyl Ethers to Access Ethers of Chiral Dialkyl Carbinols

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(18), P. 10411 - 10421

Published: April 26, 2023

Site- and enantio-selective alkyl-alkyl bond formation is privileged in the retrosynthetic analysis due to universality of sp3-hybridized carbon atoms organic molecules. Herein, we report a nickel-catalyzed remote asymmetric hydroalkylation alkenyl ethers via synchronous implementation alkene isomerization enantioselective C(sp3)-C(sp3) formation. Regression catalyst structure-activity relationships accelerates rational ligand modification through modular regulation. This reaction has several advantages for synthesizing chiral dialkyl carbinols their ether derivatives, including broad substrate scope, good functional group tolerance, excellent regioselectivity (>20:1 regioisomeric ratio), high enantioselectivity (up 95% enantiomeric excess).

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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NiH-catalysed proximal-selective hydroalkylation of unactivated alkenes and the ligand effects on regioselectivity

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

Published: April 7, 2022

Abstract Alkene hydrocarbonation reactions have been developed to supplement traditional electrophile-nucleophile cross-coupling reactions. The branch-selective hydroalkylation method applied a broad range of unactivated alkenes remains challenging. Herein, we report NiH-catalysed proximal-selective access β- or γ-branched alkyl carboxylic acids and β-, γ- δ-branched amines. A iodides bromides with different functional groups can be installed excellent regiocontrol availability for site-selective late-stage functionalization biorelevant molecules. Under modified reaction conditions NiCl 2 (PPh 3 ) as the catalyst, migratory takes place provide (rather than γ-) branched products. keys success are use aminoquinoline picolinamide suitable directing combined experimental computational studies ligand effects on regioselectivity detailed mechanisms.

Language: Английский

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Ligand Relay Catalysis Enables Asymmetric Migratory Reductive Acylation of Olefins or Alkyl Halides

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(47), P. 21448 - 21456

Published: Nov. 17, 2022

Design of ligands in transition-metal catalyzed reactions is challenging, especially asymmetric transformations. With each step the catalytic cycle promoted by its privileged ligand and different steps well-connected dynamic exchange, synergistic combination multiple could potentially enhance efficiency selectivity. Now, this concept has been applied to NiH-catalyzed remote hydroacylation olefins migratory acylation alkyl halides with excellent regio- enantioselectivity, utilizing two simple ligands, one for chain-walking other acylation. Starting from abundant alkenes/alkyl carboxylic acids, a wide range enantioenriched chiral α-aryl ketones can be efficiently accessed under mild conditions.

Language: Английский

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Orthogonal Access to α‐/β‐Branched/Linear Aliphatic Amines by Catalyst‐Tuned Regiodivergent Hydroalkylations

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(34)

Published: June 21, 2022

Abstract Linear, α‐branched, and β‐branched aliphatic amines are widespread in pharmaceuticals, agrochemicals, fine chemicals. Thus, the development of direct efficient methods to these structures a tunable manner is highly desirable yet challenging. Herein, catalyst‐controlled synthesis linear from Ni/Co‐catalyzed regio‐ site‐selective hydroalkylations alkenyl with alkyl halides developed. This catalytic protocol features reliable prediction control coupling position alkylation provide orthogonal access identical starting materials. platform unlocks reactivity selectivity nickel hydride cobalt chemistry catalytically repurpose three types under mild conditions.

Language: Английский

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Nickel-Catalyzed Regio- and Enantioselective Hydroamination of Unactivated Alkenes Using Carbonyl Directing Groups

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(20), P. 9091 - 9100

Published: May 11, 2022

The asymmetric addition of an N–H bond to various alkenes via a direct catalytic method is powerful way synthesizing value-added chiral amines. Therefore, the enantio- and regioselective hydroamination unactivated remains appealing goal. Here, we report highly Ni-catalyzed readily available bearing weakly coordinating native amides or esters. This succeeds for both terminal internal has broad amine coupling partner scope. mild reaction process well suited late-stage functionalization complex molecules potential gain modular access enantioenriched β- γ-amino acid derivatives 1,2- 1,3-diamines. Mechanistic studies reveal that bisoxazoline-bound Ni specie effectively leverages carbonyl coordination achieve NiH insertion into alkenes.

Language: Английский

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Regio- and enantioselective remote hydroarylation using a ligand-relay strategy

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

Published: May 5, 2022

Abstract The design of a single complicated chiral ligand to well-promote each step an asymmetric cascade reaction is sometimes formidable challenge in transition metal catalysis. In this work, highly regio- and enantioselective Ni-catalysed migratory hydroarylation relay process has been achieved with the combination two simple ligands, one which accomplishes chain-walking other causing arylation. This formal C(sp 3 )−H arylation provides direct access wide range structurally diverse 1,1-diarylalkanes, structural unit found number bioactive molecules. value strategy was further demonstrated by 1,3-arylboration.

Language: Английский

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Control of Axial Chirality through NiH-Catalyzed Atroposelective Hydrofunctionalization of Alkynes

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(6), P. 3841 - 3846

Published: March 3, 2023

Catalytic asymmetric hydrofunctionalization of alkenes is a well-established method with which to construct complex C(sp3)-enriched molecules central chirality. In contrast, the use catalytic abundant alkyne substrates produce valuable multisubstituted axial chirality remains largely unexplored. Here, we report general procedure this type catalyzed by Ni(II) salts and employing structurally simple chiral PyrOx ligand. A wide variety diverse atropisomeric styrenes have been obtained from hydroarylation alkynes high efficiency, complete Z-selectivity, excellent enantioselectivity.

Language: Английский

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Nickel-Catalyzed Migratory Cross-Coupling Reactions: New Opportunities for Selective C–H Functionalization

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(23), P. 3475 - 3491

Published: Nov. 16, 2023

ConspectusMigratory cross-coupling via metal migration is a process of significant academic and industrial interest. It provides an attractive alternative for the selective installation functional group at remote C-H positions from simple precursors, thus enabling direct synthesis challenging structures not accessible with traditional cross-coupling. In particular, merger 1,n-Ni/H shift nickel, Ni-catalyzed migratory functionalization precursors has undergone particularly intense development emerged as valuable field research in past few years. This Account will outline recent progress made this arena terms migration-functionalization modes, diverse functionalizations, strategies regio- stereocontrol. Mechanistic studies synthetic applications are also discussed.In detail, we systematically categorize our work into two parts based on modes. first part, platform created sp3 alkenes or alkyl halides iterative 1,2-Ni/H shift-selective The key reactive Ni(II)H species chain-walking could be generated situ either polarity-reversed fashion relying stoichiometric reductants (X-Ni(II)-H) redox-neutral participation nucleophilic coupling partners (FG-Ni(II)-H). One advantage associated NiH system use relatively stable, abundant, safe olefin surrogates instead sensitive organometallics required reactions. Another that including carbonation more amination thiolation smoothly achieved suitable electrophiles their precursors. Finally, to address multifaceted selectivity reactivity issues asymmetric reactions, have developed feasible ligand relay catalytic strategy. dynamic exchange process, one promotes rapid while other highly stereoselective coupling. innovative strategy overcomes formidable challenge stemming difficulty designing single efficiently promote both steps second new sp2 1,4-Ni/H been reported. Starting readily available aryl vinyl partners, situ-generated aryl- vinylnickel(II) undergo reversible along backbone, subsequent various would allow access 1,4-migratory products. success was discovery appropriate A vinyl-to-aryl successfully enables modular ipso/ortho difunctionalization aryl-to-vinyl functionalized trisubstituted alkenes.We hope inspire broad interest future We strongly believe continued efforts fascinating overcome many remaining challenges, cutting-edge ligand/catalyst design enhance selectivity, conceptually modes additional transformations, in-depth mechanistic rational reaction design.

Language: Английский

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