Generation and transformation of α-oxy carbene intermediates enabled by copper-catalyzed carbonylation

Green Carbon, Год журнала: 2024, Номер 2(1), С. 70 - 80

Опубликована: Янв. 11, 2024

Since the Fischer-Tropsch reaction was discovered by Otto Roelen in 1938, transition metal-catalyzed carbonylation reactions come as one of most important methods for preparing carbonyl-containing and carbon chain-increased compounds. As a result, field research has received considerable attention over past decades continues to increase. With continuous development in-depth study mechanism, more mechanistic details variations have been revealed, which provide possibilities organic synthesis. Recently, copper catalysis introduced carbonylative functionalization alkenes, thus enabling rapid assembly functionalized carbonyl compounds from simple starting materials. In this Account, we summarize new findings Cu-catalyzed borocarbonylation alkenes based on generation transformation α-oxy carbene intermediates. We believe that results presented Account will further inspire design reactions.

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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Engaging Alkenes in Metallaphotoredox: A Triple Catalytic, Radical Sorting Approach to Olefin-Alcohol Cross-Coupling

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(18), С. 12300 - 12309

Опубликована: Апрель 24, 2024

Metallaphotoredox cross-coupling is a well-established strategy for generating clinically privileged aliphatic scaffolds via single-electron reactivity. Correspondingly, expanding metallaphotoredox to encompass new C(

Язык: Английский

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Photocatalytic Generation of Aminium Radical Cations for C–N Bond Formation

ACS Catalysis, Год журнала: 2020, Номер 10(20), С. 11712 - 11738

Опубликована: Сен. 11, 2020

Aminium radical cations have been extensively studied as electrophilic aminating species that readily participate in C–N bond forming processes with alkenes and arenes. However, their utility synthesis has limited, generation required unstable, reactive starting materials harsh reaction conditions. Visible-light photoredox catalysis emerged a platform for the mild production of aminium from either unfunctionalized or N-functionalized amines. This Perspective covers recent synthetic methods rely on photocatalytic formation, specifically context alkene hydroamination, arene C–H amination, mesolytic cleavage alkoxyamines.

Язык: Английский

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Cobalt‐Catalyzed Radical Hydroamination of Alkenes with N‐Fluorobenzenesulfonimides

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(49), С. 25949 - 25957

Опубликована: Сен. 25, 2021

An efficient and general radical hydroamination of alkenes using Co(salen) as catalyst, N-fluorobenzenesulfonimide (NFSI) its analogues both nitrogen source oxidant was successfully disclosed. A variety alkenes, including aliphatic styrenes, α, β-unsaturated esters, amides, acids, well enones, were all compatible to provide desired amination products. Mechanistic experiments suggest that the reaction underwent a metal-hydride-mediated hydrogen atom transfer (HAT) with alkene, followed by pivotal catalyst controlled SN 2-like pathway between in situ generated organocobalt(IV) species nitrogen-based nucleophiles. Moreover, virtue modified chiral cobalt(II)-salen an unprecedented asymmetric version also achieved good excellent level enantiocontrol. This novel C-N bond construction opens new door for challenging hydrofunctionalization.

Язык: Английский

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Cobalt-catalysed enantioselective C(sp3)–C(sp3) coupling

Nature Catalysis, Год журнала: 2021, Номер 4(10), С. 901 - 911

Опубликована: Окт. 20, 2021

Язык: Английский

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NiH-Catalyzed Proximal-Selective Hydroamination of Unactivated Alkenes

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(48), С. 20470 - 20480

Опубликована: Ноя. 18, 2020

Reported herein is a modular, NiH-catalyzed system capable of proximal-selective hydroamination unactivated alkenes with diverse amine sources. The key to the successful implementation this approach promotion NiH insertion into even highly substituted olefins via coordination bidentate directing group nickel complex. A wide range primary and secondary amines can be installed in both internal terminal excellent regiocontrol under optimized reaction conditions. This protocol flexible general for preparation variety valuable β- γ-amino acid building blocks that would otherwise difficult synthesize. utility transformation was further demonstrated by site-selective late-stage modification complex medicinally relevant molecules. Combined experimental computational studies illuminate detailed mechanism.

Язык: 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, Год журнала: 2021, Номер 143(35), С. 14089 - 14096

Опубликована: Авг. 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.

Язык: Английский

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Electrochemical Synthesis of Allylic Amines from Terminal Alkenes and Secondary Amines

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(51), С. 21503 - 21510

Опубликована: Дек. 16, 2021

Allylic amines are valuable synthetic targets en route to diverse biologically active amine products. Current allylic C–H amination strategies remain limited with respect the viable N-substituents. Herein, we disclose a new electrochemical process prepare aliphatic by coupling two abundant starting materials: secondary and unactivated alkenes. This oxidative transformation proceeds via generation of an electrophilic adduct between thianthrene alkene substrates. Treatment these adducts nucleophiles base provides products in high yield. strategy is also amenable functionalization feedstock gaseous alkenes at 1 atm. In case 1-butene, Z-selective crotylation observed. strategy, however, not synthesis simple building blocks; complex molecules suitable as both partners. Preliminary mechanistic studies implicate vinylthianthrenium salts key reactive intermediates.

Язык: Английский

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Enantioselective NiH‐Catalyzed Reductive Hydrofunctionalization of Alkenes

Chinese Journal of Chemistry, Год журнала: 2021, Номер 40(5), С. 651 - 661

Опубликована: Дек. 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.

Язык: Английский

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