Overcoming limitations in non-activated alkene cross-coupling with nickel catalysis and anionic ligands

Nature Catalysis, Год журнала: 2024, Номер 7(11), С. 1154 - 1164

Опубликована: Авг. 15, 2024

Язык: Английский

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Ligand-modulated nickel-catalyzed regioselective silylalkylation of alkenes

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Ноя. 23, 2023

Organosilicon compounds have shown tremendous potential in drug discovery and their synthesis stimulates wide interest. Multicomponent cross-coupling of alkenes with silicon reagents is used to yield complex silicon-containing from readily accessible feedstock chemicals but the reaction simple remains challenging. Here, we report a regioselective silylalkylation alkenes, which enabled by using stable Ni(II) salt an inexpensive trans-1,2-diaminocyclohexane ligand as catalyst. Remarkably, this can tolerate broad range olefins bearing various functional groups, including alcohol, ester, amides ethers, thus it allows for efficient selective assembly diverse bifunctional organosilicon building blocks terminal alkyl halides Suginome reagent. Moreover, expedient synthetic route toward alpha-Lipoic acid has been developed methodology.

Язык: Английский

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Ni-Catalyzed 1,1- and 1,3-Aminoboration of Unactivated Alkenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(50), С. 27254 - 27261

Опубликована: Дек. 11, 2023

Alkene borylfunctionalization reactions have emerged as useful methods for chemical synthesis. While much progress has been made on 1,2-borylamination reactions, the related 1,1- and 1,3-borylaminations not reported. Herein, a Ni-catalyzed 1,1-borylamination of 1,1-disubstituted monosubstituted alkenes 1,3-borylamination cyclic are presented. Key to development these was identification an alkyllithium activator in combination with Mg salts. The utility products mechanistic details discussed.

Язык: Английский

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Pd(0)-Catalyzed Diastereoselective and Enantioselective Intermolecular Heck–Miyaura Borylation of Internal Enamides for the β-Aminoboronate Ester Synthesis

ACS Catalysis, Год журнала: 2023, Номер 14(1), С. 418 - 425

Опубликована: Дек. 20, 2023

Miyaura borylation is widely recognized as one of the most reliable methods for constructing an organoboron compound. Reported herein Pd(0)-catalyzed asymmetric three-component Heck–Miyaura with interception internal olefin, aryldiazonium salt, and diboron reagent. This Heck-triggered protocol proceeds in a highly chemoselective, diastereoselective, enantioselective manner, thus allowing expedient construction 1,2-diaryl substituted β-aminoboronate esters derivatives vicinal stereogenic centers. The versatility resulting benzylic boronic allows their further transformation to more-intricate chiral amines.

Язык: Английский

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Recent Advances in Nonprecious Metal Catalysis

Organic Process Research & Development, Год журнала: 2024, Номер 28(4), С. 937 - 948

Опубликована: Март 21, 2024

Significant emphasis has been placed on the development of nonprecious metal alternatives to precious-metal-catalyzed reactions due lower cost and greater sustainability they can achieve. This review is part a series describing advances in nonprecious-metal-catalyzed transformations published between March June 2023 that are relevant pharmaceutical process chemistry.

Язык: Английский

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Enantioselective Cobalt-Catalyzed Remote Hydroboration of Alkenylboronates

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 14, 2025

Heteroatomic groups in alkenes typically direct thermodynamically favored chain walking of C═C bonds toward themselves, thereby facilitating C-H bond functionalization near the heteroatoms. We present herein an efficient cobalt-catalyzed contra-thermodynamic remote hydroboration alkenylboronates with pinacolborane to synthesize chiral 1,n-diboronates. This protocol features a broad substrate scope, high functional group tolerance, and excellent enantioselectivity. Mechanistic studies indicate involvement chain-walking process. Gram-scale reactions various product derivatizations further highlight its practicality.

Язык: Английский

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Cobalt-Catalyzed Remote Site-Selective Hydroboration of Unactivated Alkenes via Chain-Walking Strategy

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

An expedient synthesis of α-aminoboronic acid derivatives via cobalt-catalyzed remote site-selective hydroboration unactivated alkenes is described herein. The strategy characterized by its simplicity, site-selectivity, and wide substrate scope, as both terminal internal could undergo the reaction smoothly, affording corresponding products in good yields. According to mechanism, Co-H generated from Co(acac)2 presence HBpin, which starts chain-walking a series alkene insertion β-H elimination process.

Язык: Английский

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Nickel-Catalyzed 1,1-Carboboration of Polysubstituted Internal Alkenes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

Herein, we report a nickel-catalyzed 1,1-carboboration of di- and trisubstituted alkenyl boronates through chain-walking strategy. This reaction effectively addresses the polarity-mismatch problem via ligand control, enabling coupling various carbon-based electrophiles while accommodating broad range functional groups. The approach yields diverse tetrasubstituted carbon gem-diboronate derivatives with exceptional regioselectivity. synthetic utility this method is further demonstrated concise synthesis high-value bioactive molecules.

Язык: Английский

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Metal‐catalyzed reductive alkylation of alkenes: From copper to alternative catalysts

Bulletin of the Korean Chemical Society, Год журнала: 2025, Номер 46(4), С. 413 - 421

Опубликована: Апрель 1, 2025

Abstract In recent years, transition metal‐catalyzed reductive alkylation of alkenes has gained attention due to its ability circumvent the use unstable organometallic reagents by generating reactive intermediates in situ from stable precursors with enhanced reaction safety and efficiency. This review provides an overview advancements copper‐catalyzed alkenes, a particular focus on hydrosilanes diborons as stoichiometric reducing agents. Key topics include mechanistic insights, strategies for controlling regio‐ stereoselectivity both intra‐ intermolecular reactions, innovative catalyst designs selective product synthesis. Emerging trends such radical‐mediated transformations contributions alternative first‐row metals including nickel iron are also discussed.

Язык: Английский

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Enantioselective Decarboxylative C(sp³)-C(sp³) Cross-Coupling of Aliphatic Redox-Active Esters with gem-Borazirconocene Alkanes

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

Опубликована: Сен. 17, 2024

Asymmetric decarboxylative cross-couplings of carboxylic acids are powerful methods for synthesizing chiral building blocks essential in medicinal chemistry and material science. Despite their potential, creating versatile alkylboron derivatives through asymmetric C(sp

Язык: Английский

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