Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: unknown
Published: Dec. 5, 2024
A novel electrochemical cyclization reaction of N -acryloyl-indole-3-carboxamides has been developed, which provides a new and efficient strategy for the synthesis γ-carbolinone derivatives.
Language: Английский
ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(12), P. 7513 - 7551
Published: June 9, 2021
Catalytic functionalization of alkynes with organoboron reagents provides a straightforward access to stereochemically defined multisubstituted alkenes, which are structural motifs commonly found in bioactive compounds and organic materials. Recent progress has substantially broadened the scope this field on several fronts. Strategies for regioselectivity control 1,2-migratory insertion across unsymmetrical internal alkynes, as well direct products anti-insertion stereochemistry, have been devised. The alkenyl-to-aryl 1,4-metal migration upon metal recently exploited powerful cascade sequences leading complex polycyclic scaffolds, including development enantioselective processes. Elegant enantiospecific dynamic kinetic resolution methods developed accessing chiral allenes from propargylic alcohol derivatives. Mechanistic manifolds emerged based single-electron transfer (SET) that provided fresh impetus alkyne 1,2-difunctionalization complementary stereoselectivity processes relying 1,2-insertion R–M species. Herein, we discuss most recent advances transition-metal-catalyzed using reagents, categorized according type mechanistic outcome. Emphasis is placed aspects, synthetic utility, limitations, challenges future research.
Language: Английский
Citations
148
Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(13), P. 5287 - 5299
Published: Jan. 1, 2022
This review summarizes the different applications and underlying concepts that are applied for Cu( i )- or ii )-photocatalyzed difunctionalizations of alkenes.
Language: Английский
Citations
103
Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(45), P. 20554 - 20560
Published: Oct. 28, 2022
A Pd(0)/blue light catalyzed carboiodination reaction is reported. simple, air-stable catalytic system, utilizing [Pd(allyl)Cl]2 and DPEPhos, generated a variety of iodinated hetero- carbocycles including oxindoles, dihydrobenzofurans, indolines, chromane, tetrahydronaphthalene. This protocol was tolerant sensitive functional groups free carboxylic acids, phenols, anilines, as well pyridines, while delivering products in up to 94% yield. Support for reversible C–I bond formation via single electron mechanism obtained using deuterium labeled substrate stoichiometric neopentylpalladium species.
Language: Английский
Citations
50
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 11012 - 11018
Published: May 12, 2023
A BF3-catalyzed atom-economical fluorocarbamoylation reaction of alkyne-tethered carbamoyl fluorides is reported. The catalyst acts as both a fluoride source and Lewis acid activator, thereby enabling the formal insertion alkynes into strong C-F bonds through halide recycling mechanism. developed method provides access to 3-(fluoromethylene) oxindoles γ-lactams with excellent stereoselectivity, including fluorinated derivatives known protein kinase inhibitors. Experimental computational studies support stepwise mechanism for involving turnover-limiting cyclization step, followed by internal transfer from BF3-coordinated adduct. For methylene oxindoles, thermodynamically driven Z-E isomerization facilitated transition state aromatic character. In contrast, this stabilization not relevant γ-lactams, which results in higher barrier exclusive formation Z-isomer.
Language: Английский
Citations
31
Dalton Transactions, Journal Year: 2021, Volume and Issue: 50(10), P. 3394 - 3428
Published: Jan. 1, 2021
The utility of pincer−nickel complexes in catalyzing reactions such as cross−coupling, oxidation, (de)hydrogenation, hydrofunctionalization, C−H activation and CO2 functionalization has been reviewed from a synthetic mechanistic point view.
Language: Английский
Citations
54
Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(31), P. 16750 - 16762
Published: March 1, 2021
Abstract Nickel catalysis has demonstrated the capability of performing a broad range synthetically challenging transformations over last decade. Though recent literature focused on formation C−C and C−N bonds, variety breakthroughs in field C−X bond generation have also been reported. A diverse strategies using nickel developed, an effort to expand scope synthetic utility these halogenation methods. This Minireview will cover six emerging this including: oxidatively induced reductive elimination, triflate‐to‐halogen exchange reactions, directed C−H halogenation, non‐directed electrophilic arenes, enantioselective α‐fluorination carbonyl containing compounds, 1,2‐difunctionalization‐halogenation reactions. The final section split into two parts: nickel‐catalyzed hydrohalogenation carbohalogenation
Language: Английский
Citations
47
Organic & Biomolecular Chemistry, Journal Year: 2020, Volume and Issue: 18(41), P. 8278 - 8293
Published: Jan. 1, 2020
Radical vicinal carbohalofunctionalization of C-C multiple bonds via atom transfer processes constitutes an efficient method for the construction halogenated building blocks with complete economy radical cleavage a pre-existing carbon-halogen σ-bond reagent and their transposition over π-bond alkenes alkynes. This review summarizes recent advances in photo-induced version this class transformations. A variety transition-metal complexes, organic dyes, phosphines, amines, phenols aldehydes were utilized as catalysts existing bond corresponding presence light source. Alongside 1,2-haloalkylation haloperfluoroalkylation reactions, addition (ATRA) or cyclization (ATRC) reactions aryl halides are also discussed.
Language: Английский
Citations
45
Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(9)
Published: Dec. 28, 2021
We describe here a Ni-catalyzed intermolecular carbo-fluoromethylation of alkynes with aliphatic halides and fluoromethyl (BrCF2 H ICH2 F) in the presence zinc, enabling facile selective access to diverse range biologically valuable CF2 H/CH2 F-incorporated alkenes excellent regio- stereoselectivity. Notably, merging intramolecular radical cyclization coupling enables expedient constructions lactones lactams high efficiency selectivity. Mechanistic studies disclose that this catalytic protocol proceeds via addition an alkyne followed by unit.
Language: Английский
Citations
41
ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(2), P. 925 - 931
Published: Jan. 5, 2021
A scalable nickel-catalyzed carboiodination reaction generating 6-membered carbocycles is reported. NiI2 and P(OEt)3, as the ligand reducing agent, provided decorated iodo-tetrahydronaphthalenes in up to 94% yield. The impact of varying electronic steric parameters on are reported a non-linear Hammett plot was obtained, supporting change rate-determining step from oxidative addition reductive elimination. Experimental DFT studies suggest that malonate group may stabilize nickel oxidative-addition complex. variety heteroatom-containing nucleophiles medicinally relevant heterocycles were easily incorporated into products via simple SN2 chemistry.
Language: Английский
Citations
33
Green Chemistry, Journal Year: 2022, Volume and Issue: 24(3), P. 1103 - 1108
Published: Jan. 1, 2022
A protocol for visible light-mediated selective C–Cl activation of chlorides the polychlorination alkenes has been developed. This strategy allows installation multiple chlorine atoms into double bonds under mild conditions.
Language: Английский
Citations
28