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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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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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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Palladium‐Catalyzed Inward Isomerization Hydroaminocarbonylation of Alkenes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(26)

Опубликована: Апрель 15, 2024

In contrast to the kinetically favored outward isomerization-hydrocarbonylation of alkenes, disfavored inward alkenes remains an important challenge. Herein, we have developed a novel and effective palladium-catalyzed isomerization-hydroaminocarbonylation unactivated aniline hydrochlorides for formation synthetically valuable α-aryl carboxylic amides in high yields site-selectivities. The efficiency reaction is attributed relay catalysis strategy, which Markovnikov-favored [PdH]-P

Язык: Английский

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NiH-Catalyzed Regio- and Enantioselective Hydroalkylation for the Synthesis of β- or γ-Branched Chiral Aromatic N-Heterocycles

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(40), С. 22122 - 22134

Опубликована: Сен. 25, 2023

A nickel hydride-catalyzed regio- and enantioselective hydroalkylation reaction was developed to give access a library of chiral β- or γ-branched aromatic N-heterocycles. This intriguing asymmetric transformation features excellent selectivities, step- atom-economies, generating two kinds products through one synthetic strategy. Furthermore, the possible mechanism extensively investigated using numerous control experiments density functional theory calculations.

Язык: Английский

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Selective Hydrofunctionalization of Alkenyl Fluorides Enabled by Nickel-Catalyzed Hydrogen Atoms and Group Transfer: Reaction Development and Mechanistic Study

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Апрель 15, 2024

Due to the unique effect of fluorine atoms, efficient construction high-value alkyl fluorides has attracted significant interest in modern drug development. However, enantioselective catalytic strategies for assembly highly functionalized chiral C(sp

Язык: Английский

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Palladium-Catalyzed Enantioselective Multicomponent Cross-Coupling of Trisubstituted Olefins

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(24), С. 16892 - 16901

Опубликована: Июнь 6, 2024

The development of a catalytic method for stereogenic carbon center formation holds immense significance in organic synthesis. Transition-metal-catalyzed cross-coupling reaction has been regarded as straightforward and efficient tool stereoselectively forging C–C bond. Nevertheless, the creation acyclic all-carbon quaternary-containing vicinal stereocenters remains notoriously challenging within domain chemistry despite their prominence various bioactive small molecules. Herein, we describe palladium-catalyzed asymmetric multicomponent trisubstituted alkene with aryl diazonium salts arylboronic acids to realize tertiary-quaternary centers high regio-, distereo-, enantioselectivity. Specifically, precise manipulation stereoconfiguration alkenes enables divergent stereoselective reaction, thus allowing facile construction all four enantiomers. Harnessing ligand-swap strategy involving chiral bisoxazoline an achiral fumarate individually accelerates enantioselective migratory insertion reductive elimination step process, supported by density functional theory (DFT) calculations, obviating requirement neighboring directing group internal olefin skeleton.

Язык: Английский

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Hydrodeuteroalkylation of Unactivated Olefins Using Thianthrenium Salts

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(36)

Опубликована: Июнь 13, 2024

Isotopically labeled alkanes play a crucial role in organic and pharmaceutical chemistry. While some deuterated methylating agents are readily available, the limited accessibility of other deuteroalkyl reagents has hindered synthesis corresponding products. In this study, we introduce nickel-catalyzed system that facilitates various deuterium-labeled through hydrodeuteroalkylation d2-labeled alkyl TT salts with unactivated alkenes. Diverging from traditional reagents, thianthrenium (TT) can effectively selectively deuterium at α position chains using D

Язык: Английский

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Enantioselective alkene hydroalkylation overcoming heteroatom constraints via cobalt catalysis

Nature Synthesis, Год журнала: 2024, Номер 3(9), С. 1134 - 1144

Опубликована: Июль 10, 2024

Язык: Английский

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NiH-catalyzed C–N bond formation: insights and advancements in hydroamination of unsaturated hydrocarbons

Chemical Science, Год журнала: 2023, Номер 15(2), С. 442 - 457

Опубликована: Дек. 6, 2023

The formation of C-N bonds is a fundamental aspect organic synthesis, and hydroamination has emerged as pivotal strategy for the synthesis essential amine derivatives. In recent years, there been surge interest in metal hydride-catalyzed reactions common alkenes alkynes. This method avoids need stoichiometric organometallic reagents overcomes problems associated with specific compounds that may impact functional group compatibility. Notably, developments have brought to forefront olefinic hydroamidation facilitated by nickel hydride (NiH) catalysis. inclusion suitable chiral ligands paved way realization asymmetric realm olefins. review aims provide an in-depth exploration latest achievements bond through intermolecular catalyzed hydrides. Leveraging this innovative approach, diverse range alkene alkyne substrates can be efficiently transformed into value-added enriched bonds. intricacies are succinctly elucidated, offering concise overview underlying reaction mechanisms. It our aspiration comprehensive will stimulate further progress NiH-catalytic techniques, fine-tune systems, drive innovation catalyst design, foster deeper understanding

Язык: Английский

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