Chromium‐Catalyzed Reductive Cross‐Coupling to Construct C−SS Bonds from Unactivated Alkyl Electrophiles

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(15)

Published: March 15, 2024

Abstract Low‐valent chromium catalysts are cheap and less toxic compared to other transition metal catalysts. Here in, we reported a ligand‐free chromium(III)‐catalyzed manganese reductive cross‐coupling of unactivated alkyl electrophiles, such as sulfonates chlorides, with trisulfide dioxides thiolation agents form carbon−sulfur bonds. The powerful method featured ample substrate scope wide functional group tolerance, constructing large number unsymmetrical disulfides under simple conditions.

Language: Английский

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Photo-induced ring-maintaining hydrosilylation of unactivated alkenes with hydrosilacyclobutanes

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 12, 2025

Abstract Increasing attention has been paid to silacyclobutanes because of their wide application in ring opening and extension reactions. However, the synthesis functionalized remains an unmet challenge limited functional group tolerance reactions with organometallic reagents chlorosilacyclobutanes. Herein, we report a conceptually different solution this end through visible-light-induced metal-free hydrosilylation unactivated alkenes hydrosilacyclobutanes. A range diverse groups including base-sensitive acid, alcohol ketones participated reaction smoothly. In particular, first dihydrosilacyclobutane provides facile access various alkyl monohydrosilacyclobutanes. Unsymmetrical dialkyl have also synthesized consecutive one pot. The mechanism study reveals that Lewis basic solvent could promote generation strained silyl radicals by direct light irradiation without redox-active photocatalyst thiol catalyst plays important role accelerating reaction.

Language: Английский

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Rhodium-Catalyzed Hydrolytic Cleavage of the Silicon–Carbon Bond of Silacyclobutanes to Access Silanols

Organic Letters, Journal Year: 2023, Volume and Issue: 25(39), P. 7186 - 7191

Published: Sept. 27, 2023

Herein, we report the first rhodium-catalyzed hydrolytic cleavage of silicon–carbon bond in silacyclobutanes using water as reactant. A series could be employed this reaction presence Rh/BINAP complex, resulting corresponding silanols good yields. Additionally, a chiral 1,1,4,4-tetraaryl-2,3-O-isopropylidene-l-threitol-derived phosphoramidite ligand used to yield Si-stereogenic silanol with promising enantioselectivity.

Language: Английский

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Nickel(0)-catalyzed ring-opening reaction of silacyclobutanes with 1,3-dienes to access allylsilane

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(14), P. 3821 - 3826

Published: Jan. 1, 2024

Here we report a Ni-catalyzed highly regio- and stereoselective ring opening reaction of SCBs with 1,3-dienes for straightforward facile preparation allylsilanes.

Language: Английский

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Palladium-catalyzed double activation of Si-C(sp3) bond of benzosilacyclobutenes synergized with unexpected olefin migration and ring-opening hydrolysis

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 440, P. 115788 - 115788

Published: Oct. 10, 2024

Language: Английский

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Nickel‐Catalyzed Reductive Protocol To Access Silacyclobutanes with Unprecedented Functional Group Tolerance

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(47)

Published: Aug. 22, 2024

Abstract While significant progress has been made in the area of transition metal‐catalyzed ring‐opening and formal cycloaddition reactions 1,1‐disubstituted silacyclobutanes (SCBs), synthesizing these SCBs—particularly those bearing additional functional groups—continues to present synthetic challenges. In this context, we a novel Ni‐catalyzed reductive coupling reaction that combines 1‐chloro‐substituted with aryl or vinyl halides pseudohalides, thereby obviating need for organometallic reagents. This method facilitates generation remarkable tolerance various groups. approach serves as complementary more step‐economical alternative commonly used yet moisture‐ air‐sensitive nucleophilic substitution involving Grignard lithium Our initial mechanistic studies indicate is initiated by oxidative cleavage Si−Cl bond 1‐chlorosilacyclobutanes, which represents distinct mechanism from previously documented processes carbon electrophiles chlorosilanes.

Language: Английский

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Nickel‐Catalyzed Reductive Protocol To Access Silacyclobutanes with Unprecedented Functional Group Tolerance

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(47)

Published: Aug. 22, 2024

Abstract While significant progress has been made in the area of transition metal‐catalyzed ring‐opening and formal cycloaddition reactions 1,1‐disubstituted silacyclobutanes (SCBs), synthesizing these SCBs—particularly those bearing additional functional groups—continues to present synthetic challenges. In this context, we a novel Ni‐catalyzed reductive coupling reaction that combines 1‐chloro‐substituted with aryl or vinyl halides pseudohalides, thereby obviating need for organometallic reagents. This method facilitates generation remarkable tolerance various groups. approach serves as complementary more step‐economical alternative commonly used yet moisture‐ air‐sensitive nucleophilic substitution involving Grignard lithium Our initial mechanistic studies indicate is initiated by oxidative cleavage Si−Cl bond 1‐chlorosilacyclobutanes, which represents distinct mechanism from previously documented processes carbon electrophiles chlorosilanes.

Language: Английский

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Recent Advances in Visible Light Photocatalytic and Transition Metal-Catalyzed Synthesis of Disulfide Compounds

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Reviewing photocatalytic and metal-catalyzed disulfide synthesis, 2021–2024, emphasizes efficiency, selectivity, sustainability for drug material science.

Language: Английский

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