Copper-Catalyzed Radical Relay 1,3-Carbocarbonylation across Two Distinct C═C Bonds

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3014 - 3019

Published: March 28, 2024

The radical relay provides an effective paradigm for intermolecular assembly to achieve functionalization across remote chemical bonds. Herein, we report the first 1,3-carbocarbonylation of α-carbonyl alkyl bromides two separate C═C reaction is highly chemo- and regioselective, with C(sp3)–C(sp3) bonds one C═O bond formed in a single orchestrated operation. In addition, synthesis method under mild conditions using inexpensive copper as catalyst allows facile access structurally diverse products. plausible mechanism investigated through series control experiments, including trapping, clock critical intermediate 18O labeling experiment.

Language: Английский

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Visible-light-promoted radical cyclisation of unactivated alkenes in benzimidazoles: synthesis of difluoromethyl- and aryldifluoromethyl-substituted polycyclic imidazoles

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 234 - 241

Published: Jan. 30, 2025

An efficient and eco-friendly approach for synthesizing difluoromethyl- aryldifluoromethyl-substituted polycyclic imidazoles was established via a visible-light-promoted radical cyclization reaction. This method employed the readily accessible inexpensive CF 2 HCO H or PhCF COOH, along with benzimidazoles bearing unactivated alkenes PhI(OAc) as substrates, proceeded without need of any base, metal catalyst, photocatalyst additive. In total, 24 examples were examined, all them successfully underwent reaction to produce target products in good excellent yields. Mechanistic studies revealed that proceeds pathway.

Language: Английский

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Visible-light-induced decarboxylative cascade cyclization of acryloylbenzamides with N-hydroxyphthalimide esters via EDA complexes

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(5), P. 965 - 969

Published: Jan. 1, 2024

A visible-light-induced, electron donor–acceptor (EDA) complex-enabled decarboxylative cascade reaction of acryloylbenzamides with alkyl N -hydroxyphthalimide esters by NaI/PPh 3 catalysis was developed.

Language: Английский

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Pentafluorosulfanylation of Acrylamides: The Synthesis of SF₅-Containing Isoquinolinediones with SF₅Cl

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(21), P. 15941 - 15952

Published: Oct. 24, 2024

We disclose herein an efficient and facile method for the synthesis of SF5-containing isoquinolinediones with all-carbon quaternary stereocenter via intramolecular pentafluorosulfanylation acrylamides using SF5Cl as a reagent. The protocol proceeds under mild reaction conditions enjoys broad substrate scope, wide functional group compatibility, high atom- step-economy. A radical mechanism involving SF5 cascade addition/cyclization is proposed.

Language: Английский

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Recent developments for the synthesis of the dihydroisoquinolin-1(2H)-ones via cyclization of N-allylbenzamides

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134497 - 134497

Published: Jan. 1, 2025

Language: Английский

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Photocatalytic Proton-Coupled Electron Transfer Enabled Radical Cyclization for Isoquinoline-1,3-diones Synthesis

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(7), P. 5060 - 5068

Published: March 25, 2024

Radical cyclization has been demonstrated to be an efficient method access functionalized heterocycles from easily accessible raw materials. Described herein is the development of a photocatalytic proton-coupled electron transfer (PCET) strategy for synthesis isoquinoline-1,3-diones using readily prepared naphthalimide (NI)-based organic photocatalysts. The process features free metal-complex photocatalysts, acids, and mild reaction conditions. This radical protocol broad substrate scope can effectively applied variety medicinally relevant substrates. Furthermore, control experiments were conducted elucidate mechanism this visible light-induced methodology.

Language: Английский

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Copper-Catalyzed Trifluoromethylthiolaton and Radical Cyclization of N-Phenylpent-4-Enamides to Construct SCF3-Substituted γ-Lactams

Catalysts, Journal Year: 2024, Volume and Issue: 14(11), P. 797 - 797

Published: Nov. 7, 2024

An efficient method involving copper-catalyzed trifluoromethylthiolation and radical cyclization of N-phenylpent-4-enamides using readily available stable AgSCF3 as the trifluoromethylthiolating reagent is described. The enables synthesis a series potential medicinally valuable trifluoromethylthio-substituted γ-lactams relative 2-oxazolidinone derivatives with broad functional group compatibility. Mechanistic investigations indicated that this reaction involved amidyl radical-initiated cascade 5-exo-trig followed by trifluoromethylthiolation, resulting in formation new C-N C-S bonds.

Language: Английский

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