Suzuki–Miyaura cross coupling reaction: recent advancements in catalysis and organic synthesis

Catalysis Science & Technology, Год журнала: 2021, Номер 11(4), С. 1186 - 1221

Опубликована: Янв. 1, 2021

Suzuki–Miyaura cross coupling reaction (SMCR) – A milestone in the synthesis of C–C coupled compounds.

Язык: Английский

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Nickel-Catalyzed Modular Four-Component 1,4-Alkylcarbonylation of 1,3-Enynes to Tetra-Substituted CF₃–Allenyl Ketones

ACS Catalysis, Год журнала: 2024, Номер 14(4), С. 2144 - 2150

Опубликована: Янв. 25, 2024

The modular four-component carbonylation of unsaturated hydrocarbons represents an elegant strategy for the one-pot synthesis complex carbonyl compounds. However, this is currently focused on 1,2-difunctionalization olefins or alkynes, and 1,4-alkylcarbonylation 1,3-enynes remains unexplored. In study, we report a Ni-catalyzed CF3-containing under 1 atm CO, which affords tetra-substituted CF3-allenyl ketones with good yields selectivity. This protocol features mild conditions, broad substrate scope, acceptable functional group compatibility. Control experiments revealed that reactivity oxime esters (regulated by leaving groups) polarity matching are crucial success cascade. Preliminary mechanistic studies suggest acyl nickel key intermediate in transformation.

Язык: Английский

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Construction of C−S and C−Se Bonds from Unstrained Ketone Precursors under Photoredox Catalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(8)

Опубликована: Янв. 8, 2024

A mild photoredox catalyzed construction of sulfides, disulfides, selenides, sulfoxides and sulfones from unstrained ketone precursors is introduced. Combination this deacylative process with S

Язык: Английский

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Cu-Catalyzed Enantioselective Alkylarylation of Vinylarenes Enabled by Chiral Binaphthyl–BOX Hybrid Ligands

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(45), С. 19017 - 19022

Опубликована: Окт. 5, 2020

Transition-metal-catalyzed radical relay coupling reactions have recently emerged as one of the most powerful methods to achieve difunctionalization olefins. However, there has been limited success in applying this method asymmetric catalysis using an effective chiral ligand. Herein we report Cu-catalyzed enantioselective alkylarylation vinylarenes alkylsilyl peroxides alkyl sources. This reaction proceeds under practical conditions and affords 1,1-diarylalkane structures that are found a variety bioactive molecules. Notably, highly was accomplished by combining bis(oxazoline) ligands with binaphthyl scaffolds.

Язык: Английский

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Deacylative Homolysis of Ketone C(sp³)–C(sp²) Bonds: Streamlining Natural Product Transformations

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 7, 2025

The homolytic cleavage of C–C bonds adjacent to specific functional groups has lately emerged as a versatile approach for molecular diversification. Despite the ubiquity and synthetic utility ketones, radical fragmentation their α-C–C proven be formidable challenge. Here, we present broadly applicable deacylative strategy designed homolytically cleave aliphatic ketones various complexities, including transformations cycloalkanones into carboxylic acids tethered C-centered free radicals that can engaged in diverse radical-based processes. method involves ketone activation through treatment with hydrogen peroxide, yielding gem-dihydroperoxides. Subsequent single-electron-transfer reduction mediated by low-valent metal complex generates alkyl captured selectively radicophile choice, catalytic cross-coupling. logic our functionalization is exemplified total synthesis 14 natural products, one analogue, two drugs starting from readily available showcasing its transformative power settings. This obviates need reagents allows controlled conversion reconstructed making process highly across spectrum domains.

Язык: Английский

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Enantioselective Remote Alkylation Enabled by Metallaphotoredox Catalysis via Selective C–C Bond Cleavage

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 2212 - 2221

Опубликована: Янв. 23, 2025

Despite recent advances in enantioselective radical coupling with strained cyclic rings, asymmetric reactions triggered by unstrained motifs remain rare. Herein, we report a mild and general strategy for activating diverse set of readily available alcohols the remote site-specific allylic alkylation ketones through combination photoredox-mediated proton-coupled electron transfer chiral chromium catalysis. This newly developed dual catalytic system exhibits extensive applicability, operates under conditions, offers straightforward operation, demonstrates tolerance to functional groups. The open-shell has also been applied late-stage modification complex drug natural product derivatives high levels enantioselectivity.

Язык: Английский

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When all C–C breaks LO–Ose

Trends in Chemistry, Год журнала: 2023, Номер 5(3), С. 174 - 200

Опубликована: Фев. 14, 2023

Organic peroxides are becoming popular intermediates for novel chemical transformations. The weak O-O bond is readily reduced by transition metals, including iron and copper, to initiate a radical cascade process that breaks C-C bonds. Great potential exists the rapid generation of complexity, originating from ability couple resulting free radicals with wide range partners. First, this review article discusses history synthesis organic peroxides, providing context necessary understand methodology. Then, it highlights 91 examples recent applications functionalization bonds accessed through metal-mediated reduction peroxides. Finally, we provide some comments about safety when working

Язык: Английский

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Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp³)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

Organometallics, Год журнала: 2023, Номер 42(18), С. 2598 - 2612

Опубликована: Март 1, 2023

The reaction of Ni(II) acetate with diacyl peroxides produces high-valence Ni-species capable catalytic oxidative acyloxylation C(sp3)–H bonds in ethers, ketones, and alkanes. desired esters were obtained 20–82% yields. Computational analysis suggests that activation the peroxide moiety a dynamically interconverting mixture formal Ni(III) state. Remarkably, these species, coordination RCO2 group at Ni preserves radical character carboxylate (i.e., acts as an “L-ligand”), so latter can induce fast C–H abstraction. spirocyclopropyl prevents premature decarboxylation via combination hybridization factors stereoelectronic effects. A variety viable patterns identified experimentally computationally.

Язык: Английский

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Copper-catalyzed alkylarylation of vinylarenes with cycloalkylsilyl peroxides and boronic acids

Chemical Communications, Год журнала: 2020, Номер 56(73), С. 10714 - 10717

Опубликована: Янв. 1, 2020

A mild copper-catalyzed alkylarylation of vinylarenes with cycloalkylsilyl peroxides and boronic acids is described. This three-component protocol provides a straightforward approach to the remote keto-functionalized 1,1-diarylmethane derivatives. radical pathway initiated by C-C bond cleavage proposed for this tandem reaction.

Язык: Английский

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Iron catalyzed ketoalkylation and ketoalkylation/etherification of styrenes initiated by selective C–C bond cleavage

Organic Chemistry Frontiers, Год журнала: 2020, Номер 7(17), С. 2414 - 2418

Опубликована: Янв. 1, 2020

A mild and efficient iron-catalyzed ketoalkyl-Heck-type coupling initiated by radical C–C bond cleavage is described. Furthermore, this concise catalytic system was also applicable for the three-component ketoalkylation/etherification of styrenes.

Язык: Английский

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