Construction of C−S and C−Se Bonds from Unstrained Ketone Precursors under Photoredox Catalysis DOI
Hao Wu, Shuguang Chen,

Chunni Liu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(8)

Published: Jan. 5, 2024

Abstract A mild photoredox catalyzed construction of sulfides, disulfides, selenides, sulfoxides and sulfones from unstrained ketone precursors is introduced. Combination this deacylative process with S N 2 or coupling reactions provides novel convenient modular strategies toward unsymmetrical symmetric disulfides. Reactivity studies favor a bromine radical that initiates HAT (Hydrogen Atom Transfer) the aminal intermediate resulting in expulsion C‐centered intercepted to make C−S C−Se bonds. Gram scale reactions, broad substrate scope tolerance towards various functional groups render method appealing for future applications synthesis organosulfur selenium complexes.

Language: Английский

Suzuki–Miyaura cross coupling reaction: recent advancements in catalysis and organic synthesis DOI
Brijesh S. Kadu

Catalysis Science & Technology, Journal Year: 2021, Volume and Issue: 11(4), P. 1186 - 1221

Published: Jan. 1, 2021

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

Language: Английский

Citations

145
Nickel-Catalyzed Modular Four-Component 1,4-Alkylcarbonylation of 1,3-Enynes to Tetra-Substituted CF3–Allenyl Ketones DOI

Qi-Chao Shan,

Yan Zhao, Shutao Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2144 - 2150

Published: Jan. 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.

Language: Английский

Citations

26
Construction of C−S and C−Se Bonds from Unstrained Ketone Precursors under Photoredox Catalysis DOI Creative Commons
Hao Wu, Shuguang Chen,

Chunni Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(8)

Published: Jan. 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

Language: Английский

Citations

21
Cu-Catalyzed Enantioselective Alkylarylation of Vinylarenes Enabled by Chiral Binaphthyl–BOX Hybrid Ligands DOI
Shunya Sakurai, Akira Matsumoto, Taichi Kano

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(45), P. 19017 - 19022

Published: Oct. 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.

Language: Английский

Citations

77
Deacylative Homolysis of Ketone C(sp3)–C(sp2) Bonds: Streamlining Natural Product Transformations DOI
Michal Šimek, Sujit Mahato,

Brady W. Dehnert

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

Citations

1
Enantioselective Remote Alkylation Enabled by Metallaphotoredox Catalysis via Selective C–C Bond Cleavage DOI
Ao Yu,

Ning Wang,

Siyuan Tang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 2212 - 2221

Published: Jan. 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.

Language: Английский

Citations

1
When all C–C breaks LO–Ose DOI Creative Commons

Jeremy H. Dworkin,

Brady W. Dehnert,

Ohyun Kwon

et al.

Trends in Chemistry, Journal Year: 2023, Volume and Issue: 5(3), P. 174 - 200

Published: Feb. 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

Language: Английский

Citations

18
Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp3)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides DOI
Vera A. Vil’, Yana A. Barsegyan, Leah Kuhn

et al.

Organometallics, Journal Year: 2023, Volume and Issue: 42(18), P. 2598 - 2612

Published: March 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.

Language: Английский

Citations

17
Copper-catalyzed alkylarylation of vinylarenes with cycloalkylsilyl peroxides and boronic acids DOI
Shuo Yang, Pin Gao,

Meng-Ting Suo

et al.

Chemical Communications, Journal Year: 2020, Volume and Issue: 56(73), P. 10714 - 10717

Published: Jan. 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.

Language: Английский

Citations

32
Iron catalyzed ketoalkylation and ketoalkylation/etherification of styrenes initiated by selective C–C bond cleavage DOI

Meng-Ting Suo,

Shuo Yang, Jun‐Cheng Yang

et al.

Organic Chemistry Frontiers, Journal Year: 2020, Volume and Issue: 7(17), P. 2414 - 2418

Published: Jan. 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.

Language: Английский

Citations

28