Nickel‐Catalyzed, Reductive C(sp³)−Si Cross‐Coupling of α‐Cyano Alkyl Electrophiles and Chlorosilanes

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(34), С. 18587 - 18590

Опубликована: Июль 2, 2021

A nickel/zinc-catalyzed cross-electrophile coupling of alkyl electrophiles activated by an α-cyano group and chlorosilanes is reported. Elemental zinc the stoichiometric reductant in this reductive process. By this, a C(sp

Язык: Английский

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Enantioselective Reductive Divinylation of Unactivated Alkenes by Nickel-Catalyzed Cyclization Coupling Reaction

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(33), С. 12961 - 12967

Опубликована: Авг. 12, 2021

Catalytic asymmetric dicarbofunctionalization of tethered alkenes has emerged as a promising tool for producing chiral cyclic molecules; however, it typically relies on aryl-tethered to form benzene-fused compounds. Herein, we report an enantioselective cross-electrophile divinylation reaction nonaromatic substrates, 2-bromo-1,6-dienes. The approach thus offers route new architectures, which are key structural motifs found in various biologically active proceeds under mild conditions, and the use t-Bu-pmrox 3,5-difluoro-pyrox ligands resulted formation divinylated products with high chemo-, regio-, enantioselectivity. method is applicable incorporation hetero- carbocycles into complex molecules.

Язык: Английский

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Switchable 1,2-Rearrangement Enables Expedient Synthesis of Structurally Diverse Fluorine-Containing Scaffolds

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(26), С. 11626 - 11637

Опубликована: Май 23, 2022

Skeletal rearrangement that changes the connectivity of molecule via cleavage and reorganization carbon–carbon bonds is a fundamental powerful strategy in complex molecular assembly. Because lack effective methods to control migratory tendency different groups, achieving switchable selectivity skeletal has been long-standing quest. Metal-based dyotropic provides unique opportunity address this challenge. However, remains unexplored. Herein, we show such problem could be solved by modifying ligands on metal catalyst changing oxidation states aptitude thereby providing ligand-controlled, strategy. Experimental density functional theory calculation studies prove rational design. The occurs only when nickel(II) intermediate reduced more nucleophilic nickel(I) species, sterically hindered iPrPDI ligand facilitates 1,2-aryl/Ni rearrangement, while terpyridine promotes 1,2-acyl/Ni rearrangement. This method allows site-selective activation C–C applied for divergent synthesis four medicinally relevant fluorine-containing scaffolds from same starting material.

Язык: Английский

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Diverse Synthesis of Chiral Trifluoromethylated Alkanes via Nickel‐Catalyzed Asymmetric Reductive Cross‐Coupling Fluoroalkylation

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(18), С. 9947 - 9952

Опубликована: Фев. 11, 2021

The trifluoromethyl group represents one of the most functional and widely used fluoroalkyl groups in drug design screening, while candidates containing chiral trifluoromethyl-bearing carbons are still few due to lack efficient methods for asymmetric introduction into organic molecules. Herein, we described a nickel-catalyzed trifluoroalkylation aryl iodides, first time, by utilizing reductive cross-coupling enantioselective fluoroalkylation. This novel method has demonstrated high efficiency, mild conditions, excellent tolerance, especially substrates diverse pharmaceutical bioactive molecules moieties. strategy provided an facile way diversity-oriented synthesis trifluoromethylated alkanes.

Язык: Английский

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Ni-Catalyzed Formal Cross-Electrophile Coupling of Alcohols with Aryl Halides

ACS Catalysis, Год журнала: 2021, Номер 11(22), С. 14102 - 14109

Опубликована: Ноя. 5, 2021

Direct coupling of unactivated alcohols remains a challenge in current synthetic chemistry. We herein demonstrate strategy building upon situ halogenation/reductive with aryl halides to forge Csp2–Csp3 bonds. The combination 2-chloro-3-ethylbenzo[d]oxazol-3-ium salt (CEBO) and TBAB as the mild bromination reagents enables rapid transformation wide range their bromide counterparts within one 5 min CH3CN DMF, which is compatible Ni-catalyzed cross-electrophile conditions presence chemical reductant. present method suitable for arylation myriad structurally complex no need prepreparation alkyl halides. More importantly, kinetically process has shown good selectivity bromination/arylation symmetric diols less sterically hindered hydroxyl groups polyols, thus offering promise selective functionalization polyols without laborious protecting/deprotecting operations. practicality this work also evident number carbohydrates, drug compounds, naturally occurring alcohols.

Язык: Английский

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