N-Heterocyclic carbenes as privileged ligands for nickel-catalysed alkene functionalisation

Chemical Society Reviews, Год журнала: 2023, Номер 52(9), С. 2946 - 2991

Опубликована: Янв. 1, 2023

This review discusses the applications of N-heterocyclic carbene ligands and their influence on reactivity selectivity Ni-catalysed alkene functionalisations.

Язык: 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, Год журнала: 2023, Номер 145(18), С. 10411 - 10421

Опубликована: Апрель 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).

Язык: Английский

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Enantioselective Hydroalkoxylation of 1,3-Dienes via Ni-Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(7), С. 3909 - 3914

Опубликована: Фев. 10, 2023

As an advance in hydrofunctionalization, we herein report that alcohols add to 1,3-dienes with high regio- and enantioselectivity. Using Ni-DuPhos, access enantioenriched allylic ethers. Through the choice of solvent-free conditions, control reversibility C–O bond formation. This work showcases a rare example methanol as reagent asymmetric synthesis.

Язык: Английский

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Ligand-Controlled Cobalt-Catalyzed Regio-, Enantio-, and Diastereoselective Oxyheterocyclic Alkene Hydroalkylation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 3405 - 3415

Опубликована: Янв. 29, 2024

Metal-hydride-catalyzed alkene hydroalkylation has been developed as an efficient method for C(sp

Язык: Английский

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Anti-Markovnikov hydroallylation reaction of alkenes via scandium-catalyzed allylic C‒H activation

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Фев. 6, 2025

Compared with rare-earth (RE)…heteroatom interaction, RE…π frequently used in facilitating regio- and stereoselectivity of olefin polymerizations, is seldomly to trigger catalytic C - H functionalization. Here, we describe a direct anti-Markovnikov hydroallylation reaction styrene derivatives 1-aryl-2-alkyl alkenes α-alkenes by use interaction. This protocol provides straightforward atom-efficient route for the synthesis valuable chain elongated internal (65 examples, up 99% yield, > 19:1 E/Z ratio). The proceeds via an allylic Csp3‒H activation pathway initiated site-selective deprotonation assistance cationic imidazolin-2-iminato scandium alkyl species followed alkene insertion into resulting scandium-allyl bond. A amount Lewis base additives, such as amine tetrahydrofuran (THF) show significant effects on reactivity selectivity. mechanism elucidated experimental studies theoretical calculations.

Язык: Английский

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Ligand‐Controlled Stereoselective Synthesis of 2‐Deoxy‐β‐C‐glycosides by Cobalt Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(22)

Опубликована: Март 17, 2023

2-Deoxy-β-C-glycosides represent an important class of carbohydrates that are present in many bioactive molecules. However, owing to the lack substituents at C2 position, stereoselective synthesis 2-deoxy-β-C-glycosides is highly challenging. Herein, we report a ligand-controlled C-alkyl glycosylation reaction access 2-deoxy-β-C-alkyl glycosides from readily available glycals and alkyl halides. This method exhibits broad substrate scope excellent diastereoselectivity under very mild conditions. In addition, unprecedented stereodivergent 2-deoxy-C-ribofuranosides achieved using different chiral bisoxazoline ligands. Mechanistic studies suggest hydrometallation glycal with bisoxazoline-ligated Co-H species may be turnover-limiting stereodetermining step this transformation.

Язык: Английский

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

Accounts of Chemical Research, Год журнала: 2023, Номер 56(23), С. 3475 - 3491

Опубликована: Ноя. 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.

Язык: Английский

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Asymmetric alkyl-alkyl cross-coupling enabled by earth-abundant metal-catalyzed hydroalkylations of olefins

Chem Catalysis, Год журнала: 2023, Номер 3(4), С. 100508 - 100508

Опубликована: Янв. 30, 2023

Язык: Английский

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Cobalt‐Catalyzed Facial‐Selective Hydroalkylation of Cyclopropenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Май 31, 2023

Abstract Cyclopropene hydrofunctionalization has been a promising strategy for accessing multi‐substituted cyclopropanes; however, cyclopropene hydroalkylation remains underdeveloped. Herein, we report low‐valent CoH‐catalyzed facial‐selective to access cyclopropanes. This reaction exhibits broad substrate scope of alkyl halides and cyclopropenes tolerates many functional groups. Moderate‐to‐good facial‐selectivity is obtained without any directing Mechanism studies provide evidence that radicals are generated from irreversible CoH insertion responsible the facial‐selectivity. Our preliminary exploration demonstrates asymmetric can be realized conspicuous auxiliary

Язык: Английский

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Enantioselective C–C cross-coupling of unactivated alkenes

Nature Catalysis, Год журнала: 2023, Номер 6(11), С. 1087 - 1097

Опубликована: Окт. 5, 2023

Язык: Английский

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