Copper-Catalyzed, Intramolecular Amination of Unactivated C(sp3)–H Bonds through Radical Relay DOI

Liyan Zuo,

Fan Yu, Shuai Zhao

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(18), P. 13077 - 13084

Published: Aug. 29, 2024

Although copper-catalyzed amination of activated C(sp3)–H bonds through radical relay has been developed, unactivated is rare. Herein, intramolecular remote reported. The reaction conducted in a mild and effective manner with moderate to good yields, demonstrating broad tolerance toward various functional groups exhibiting complete regio- chemoselectivities. This innovation supplies novel synthetic pathways for the construction saturated nitrogenated heterocycles.

Language: Английский

Redox Neutral Radical-Relay Nickel-Catalyzed Remote Carbonylation DOI
Ming Li,

Fan Gao,

Dong‐Yu Miao

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(13), P. 2306 - 2311

Published: March 29, 2023

A novel and efficient method for the catalytic installation of a carbonyl group via remote radical coupling is disclosed. The nickel-catalyzed reaction proceeds to undergo sequential single-electron transfer, 1,5-hydrogen atom insertion, thus providing α-substituted ketone. Further, this could be carried out smoothly under normal pressure redox-neutral conditions, demonstrated functional-group compatibility excellent site-selectivity.

Language: Английский

Citations

9
Copper‐Catalyzed Fluoroamide‐Directed Remote C(sp3)‐H Bond Functionalization Through Intramolecular Hydrogen Atom Transfer DOI
Xin Lv, Yuhao Yang, Liejin Zhou

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(13)

Published: Feb. 15, 2024

Abstract Direct C−H functionalization is an important strategy for the rapid synthesis of valuable organic molecules. Radical‐involved remote C(sp 3 )‐H based on hydrogen atom transfer (HAT) becomes method enabling selective direct transformation bonds at specific distal position(s). In recent years, copper‐catalyzed fluoroamide‐directed bond through intramolecular HAT has served as a robust and elegant assembly variety functionalized (sulfon)amides related derivatives. This review focuses advances in this area. These transformations proceed effectively with high selectivities good functional group compatibility under mild conditions.

Language: Английский

Citations

3
Copper-Catalyzed Hydrogen Atom Transfer and Aryl Migration Strategy for the Arylalkylation of Activated Alkenes DOI
Xi Chen, Qiang Wang, Zhe Zhang

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(24), P. 4338 - 4343

Published: June 10, 2022

Herein, we describe the copper-catalyzed arylalkylation of activated alkenes via hydrogen-atom transfer and aryl migration strategy. The reaction was carried out through a radical-mediated continuous pathway using N-fluorosulfonamides as alkyl source. primary, secondary, tertiary radicals formed by intramolecular proceeded smoothly. This methodology is an efficient approach for synthesis various amide derivatives possessing quaternary carbon center with good yields high regioselectivity.

Language: Английский

Citations

12
Fluoroamide-driven intermolecular hydrogen-atom-transfer-enabled intermolecular 1,2-alkylarylation of alkenes DOI

Chaozhihui Cheng,

De Chen,

Yang Li

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 10(4), P. 943 - 950

Published: Nov. 28, 2022

Divergent alkene 1,2-alkylarylation, 1,2-alkylamination and 1,2-alkoxycarbonylarylation enabled by fluoroamide-driven intermolecular hydrogen atom transfer is developed.

Language: Английский

Citations

10
Fluorosulfonamide-Directed Heteroarylation of Aliphatic C(sp3)–H Bonds DOI

Emily N. Pinter,

Zachary S. Sheldon,

Atanu Modak

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(7), P. 4757 - 4760

Published: March 13, 2023

Herein, we describe a formal dehydrogenative cross coupling of heterocycles with unactivated aliphatic amines. The resulting transformation enables the direct alkylation common by merging N-F-directed 1,5-HAT Minisci chemistry, leading to predictable site selectivity. reaction provides route for simple alkyl amines value-added products under mild conditions, making this an attractive option C(sp3)-H heteroarylation.

Language: Английский

Citations

5
Hybrid Catalysts from Copper Biosorbing Bacterial Strains and Their Recycling for Catalytic Application in the Asymmetric Addition Reaction of B2(pin)2 on α,β-Unsaturated Chalcones DOI Open Access
Raffaella Gandolfi, Giorgio Facchetti, Lucia Cavalca

et al.

Catalysts, Journal Year: 2022, Volume and Issue: 12(4), P. 433 - 433

Published: April 11, 2022

The recycling of heavy metal contaminants from wastewater as a source valuable products perfectly fits with the principles Circular Economy system in view restoring pollutants back into endowed new social and economic benefits. Heavy metals are often present such low concentration that it makes removal efficiency difficult to realize through conventional physicochemical methods high selectivity. Biosorption, conversely, by EPSs (extracellular polymeric substances) produced several bacterial cells’ strains, is gaining great deal attention an economic, efficient sustainable depolluting process cations copper. Metal coordination EPS components was thus deeply investigated 1H NMR titration experiments. 1,10–Phenanthroline–copper complex exploited for quantifying ability different strains sequester copper practical UV-Vis spectrophotometric method. obtained data distinguished Serratia plymuthica strain SC5II displaying copper-adsorbing properties higher than any other, Stenotrophomonas sp. 13a resulting worst one. Different analytical techniques, i.e., Dynamic Light Scattering (DLS), FT-IR analysis SEM spectroscopy were employed rationalize these results. Finally, chelates successfully hybrid catalysts asymmetric boron addition α,β-unsaturated chalcones synthesis pharmaceutical intermediates, placing waste management circular perspective.

Language: Английский

Citations

7
Copper-catalyzed regioselective C−H alkylation of phenol derivatives with unactivated alkyl chlorides: Manifesting a Cu(I)/Cu(III) pathway DOI

Suryadev K. Verma,

Benudhar Punji

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 430, P. 115351 - 115351

Published: Feb. 1, 2024

Language: Английский

Citations

1
On the Existence and Relevance of Copper(III) Fluorides in Oxidative Trifluoromethylation DOI
Noel Nebra, Daniel Joven‐Sancho

Synlett, Journal Year: 2024, Volume and Issue: unknown

Published: June 24, 2024

Abstract Numerous reports invoke CuIII–F intermediates engaging in oxidative cross-couplings mediated by low/mid-valent copper and formal sources of ‘F+’ oxidants. These elusive typically instable CuIII fluorides have been rarely characterized or spectroscopically identified, making their existence participation within catalytic cycles somehow questionable. We authenticated a stable organocopper(III) fluoride that undergoes Csp–CF3 bond formation upon addition silyl-capped alkynes following 2 e– CuIII/CuI redox shuttle. This finding strongly supports the intermediacy C–C coupling. review herein state art about well-defined enabling cross-coupling reactions. 1 Introduction Brief History Coupling-Competent Fluorides 3 Design an Isolable – yet Reactive Organocopper(III) Fluoride 4 Alkyne Trifluoromethylation: Scope Mechanism 5 Extension to Aryl–CF3 C–Heteroatom Couplings 6 Summary Outlook

Language: Английский

Citations

1
Recent Advances in Copper‐Catalyzed Functionalization of Unactivated C(sp3)−H Bonds DOI
Neha Deshpande,

Piyushkumar Satani,

Akshay Bharodiya

et al.

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(12)

Published: Oct. 31, 2022

Abstract C(sp 3 )−H functionalization is a core part of organic chemistry because the presence bonds in various molecules. However, since most are non‐reactive, their an uphill task. Standard methods employ pre‐functionalized reactants, expensive organometallic reagents, strong acids or bases and similar other harsh reaction conditions. These eventually affect prevent it from yielding optimum results. Transition metal‐based catalysts like Pd, Rh Ru provide direct route without unwanted pre‐functionalization steps. furnish superior results under mild But, expense, toxicity low natural abundance them achieving ideality. Therefore, 3d transition metal Mn, Fe, Co, Ni Cu have gained significance as alternative for conventional due to high abundance, affordability. Copper‐based particularly important owing wide range oxidation states copper facile tunability catalytic properties. Hence, immense amount research being conducted on activity functionalization. This review aims detailed overview some recent reports using systems based copper.

Language: Английский

Citations

4
Visible-light induced photocatalyst-free difluoromethylation of quinoxalinones with difluorosulfones DOI Creative Commons
Linlin Shi, Tiantian Li, Wenjing Zhang

et al.

Green Synthesis and Catalysis, Journal Year: 2023, Volume and Issue: unknown

Published: Aug. 1, 2023

Visible-light induced direct C–H difluoromethylation of quinoxalinones with 2-((difluoromethyl)sulfonyl)benzo[d]thiazole has been developed for the first time. A broad range were well tolerated and reacted difluorosulfone smoothly to give corresponding products in moderate good yields. Notably, no external photocatalyst or oxidant was required, which provides a practical green protocol access difluoromethylated quinoxalinones. Finally, control experiments demonstrated radical mechanism, density functional theory (DFT) calculations indicated radicals generated through formation an electron donor−acceptor (EDA) complex.

Language: Английский

Citations

2