Nickel-catalyzed cross-electrophile couplings of aryl fluorosulfates with vinyl chlorosilanes

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 437, P. 115636 - 115636

Published: July 6, 2024

Language: Английский

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Cross-Electrophile Silylation of Aryl Carboxylic Esters with Hydrochlorosilanes by SiH-Directed and Cr-Catalyzed Couplings

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(18), P. 12062 - 12073

Published: Aug. 29, 2023

The formation of silicon–carbon bonds through the selective coupling two strong electrophilic has been less developed. We report here silylation reactions that proceed by Si–Cl/C–O in a process is promoted chromium catalysis via α-agostic SiH → Cr interactions, allowing Si–C under ambient conditions. occur inexpensive hydrochlorosilanes with unactivated aryl carboxylic esters to give arylated hydrosilanes, while suppressing side hydride-mediated reduction achieving high chemoselectivity. In addition monosilylation, both geminal Si–Cl hydrodichlorosilanes couple C–O smoothly afford and achieve double silylations. disilanes diesters also described. Experimental theoretical studies suggest initiates reaction hydrochlorosilane Cr, which interaction group stabilizes related intermediate transition state, leading cleavage bond low barrier silachromate. Further breaking an occurs along agostic interaction, may serve as rate-determining step silylation. observation normal second-order kinetic isotope effect indicates on rates coupling. Because reactive groups are retained silylation, approach provides viable strategy access tetraorganosilane motifs late-stage hydrofunctionalization.

Language: Английский

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Palladium‐Catalyzed Cyclization/Alkenylation of Ynone Oximes with Vinylsilanes for the Assembly of Isoxazolyl Vinylsilanes

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: 19(6)

Published: Jan. 15, 2024

Abstract A palladium‐catalyzed cascade cyclization/alkenylation for the assembly of synthetically valuable isoxazolyl vinylsilane derivative has been accomplished. Easily accessible ynone oximes, and available agents were used as reaction starting materials This protocol features broad substrate scope, good functional group tolerance, step‐ atom‐economy. Remarkably, this approach provides a new construction structurally diverse isoxazolyl‐containing vinylsilanes with high molecular complexity, showing promising application in synthetic pharmaceutical chemistry.

Language: Английский

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Cobalt-catalyzed cross-electrophile coupling of alkynyl sulfides with unactivated chlorosilanes

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 27, 2024

Abstract Herein, we disclose a highly efficient cobalt-catalyzed cross-electrophile alkynylation of broad range unactivated chlorosilanes with alkynyl sulfides as stable and practical electrophiles. Strategically, employing easily synthesized precursors allows access to various alkynylsilanes in good excellent yields. Notably, this method avoids the utilization strong bases, noble metal catalysts, high temperature forcing reaction conditions, thus presenting apparent advantages, such substrate scope (72 examples, up 97% yield), Csp-S chemo-selectivity functional group compatibility (Ar-X, X = Cl, Br, I, OTf, OTs). Moreover, utilities are also illustrated by downstream transformations late-stage modification structurally complex natural products pharmaceuticals. Mechanistic studies elucidated that cobalt catalyst initially reacted sulfides, activation occurred via an S N 2 process instead radical pathway.

Language: Английский

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Aliphatic Hydrosilanes via Nickel-Catalyzed Reductive Csp³–Si Coupling of Primary Alkyl Bromides and Chlorohydrosilanes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(29), P. 6125 - 6129

Published: July 12, 2024

The reductive C-Si coupling of chlorosilanes offers efficient access to organosilanes, but its potential for constructing aliphatic ones remains largely unexplored. This manuscript presents a nickel-catalyzed Csp

Language: Английский

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Nickel-Catalyzed Cross-Electrophile Vinylation of α-Chloro Phosphonates

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(21), P. 15822 - 15833

Published: Oct. 18, 2024

Herein, we report a general and efficient Ni-catalyzed reductive cross-coupling reaction of substituted vinyl bromides α-chloro phosphonates to access set α-vinyl using zinc as the terminal reductant. This exhibits broad substrate adaptability good functional group tolerance, which allows afford diverse compounds including structurally complex motifs from natural products drugs. Furthermore, practicality was certificated through gram-scale transformation experiments. The preliminary mechanistic investigations support radical chain process. potential realize enantiomeric control makes it more valuable for further exploration.

Language: Английский

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Cobalt-Catalyzed Cross-Electrophile Coupling of Alkynyl Sulfides with Unactivated Chlorosilanes

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 29, 2024

Herein, we disclose a highly efficient cobalt-catalyzed cross-electrophile alkynylation of broad range unactivated chlorosilanes with alkynyl sulfides. Strategically, employing stable and easily synthesized sulfides as precursors allows access to various alkynylsilanes in good excellent yields. Notably, this method avoids the utilization strong bases, noble metal catalysts, high temperature forcing reaction conditions, thus presents apparent advantages, such substrate scope (72 examples, up 97% yield), Csp-S chemo-selectivity functional group compatibility (Ar-X, X = Cl, Br, I, OTf, OTs). Moreover, utilities are also illustrated by downstream transformations late-stage modification structurally complex natural products pharmaceuticals. Mechanistic studies elucidated that cobalt catalyst initially reacted sulfides, activation occurred via an S_N2 process instead radical pathway.

Language: Английский

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Electroreductive Cross-Coupling between Aromatic Aldehydes and Chlorosilanes Enabling the Synthesis of α-Silyl Alcohols

Organic Letters, Journal Year: 2024, Volume and Issue: 26(33), P. 7037 - 7042

Published: Aug. 14, 2024

α-Silyl alcohols are powerful structural motifs for pharmaceutical chemistry, materials and organic synthesis. The limitations of current synthetic techniques encompass a requirement difficult-to-obtain silyl precursors, noble-metal catalysts, narrow substrate scopes. Here, we developed general method α-silyl through electroreductive cross-coupling aldehydes chlorosilane. This features easily available reagents, mild conditions, wide scope. establishment this protocol will provide an alternative access to alcohols.

Language: Английский

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Nickel-catalyzed stereospecific reductive cross-coupling of vinyl chlorosilanes with axially chiral biaryl electrophiles

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(96), P. 14204 - 14207

Published: Jan. 1, 2024

Nickel-catalyzed stereospecific reductive cross-coupling of vinyl chlorosilanes with chiral biaryl electrophiles for the synthesis axially organosilanes.

Language: Английский

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