Diastereoselective Synthesis of Cyclopropanes from Carbon Pronucleophiles and Alkenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 16, 2023

Abstract Cyclopropanes are desirable structural motifs with valuable applications in drug discovery and beyond. Established alkene cyclopropanation methods give rise to cyclopropanes a limited array of substituents, difficult scale, or both. Herein, we disclose new cyclopropane synthesis through the formal coupling abundant carbon pronucleophiles unactivated alkenes. This strategy exploits dicationic adducts derived from electrolysis thianthrene presence substrates. We find that these dielectrophiles undergo methylene via alkenyl thianthrenium intermediates. protocol is scalable, proceeds high diastereoselectivity, tolerates diverse functional groups on both pronucleophile partners. To validate utility this procedure, prepared an substituted analogs established en route multiple pharmaceuticals.

Language: Английский

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Electrochemical Synthesis and Reactivity of Three‐Membered Strained Carbo‐ and Heterocycles

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(57)

Published: July 12, 2023

Three-membered carbocyclic and heterocyclic ring structures are versatile synthetic building blocks in organic synthesis with biological importance. Moreover, the inherent strain of these three-membered rings leads to their ring-opening functionalization through C->C, C->N, C-O bond cleavage. Traditional methods for molecules require use acid catalysts or transition metals. Recently, electro-organic has emerged as a powerful tool initiating new chemical transformations. In this review, mechanistic aspects electro-mediated carbo- heterocycles highlighted.

Language: Английский

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Electrochemical-induced solvent-tuned selective C(sp³)–H bond activation towards the synthesis of C3-functionalized chromone derivatives

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(38), P. 5050 - 5053

Published: Jan. 1, 2024

An unprecedented solvent-tuned electrochemical method for selective C(sp

Language: Английский

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Bromide-catalyzed oxo-amination of alkenes towards the synthesis of α-amine ketones under photoelectrocatalysis conditions

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(13), P. 3525 - 3530

Published: Jan. 1, 2024

An efficient and novel bromide-catalyzed oxo-amination of aryl alkenes towards the synthesis α-amine ketones under photoelectrocatalysis conditions was developed. The generation 2-bromo-1-phenylethanone supposed as key step.

Language: Английский

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Metal- and Additive-Free Intermolecular Aziridination of Olefins Using N-Boc-O-tosylhydroxylamine

Synthesis, Journal Year: 2022, Volume and Issue: 54(20), P. 4513 - 4520

Published: June 20, 2022

Abstract A metal and additive-free stereospecific direct N-H N-Me aziridination of inactivated olefins is disclosed using N-Boc-O-tosyl­hydroxylamine (TsONHBoc) as an aminating agent in hexafluoroisopropanol (HFIP). The use TsONHBoc, which generates the free situ under reaction conditions, has several inherent advantages over other similar agents, such low cost, easy access, stability (non-explosiveness) during storage a longer time.

Language: Английский

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Electrochemical-Induced C–N Bond Formation: A New Method to Synthesis (Z)-Quinazolinone Oximes Using Primary Amines and Quinazolin-4(3H)-one

Organic Letters, Journal Year: 2024, Volume and Issue: 26(6), P. 1271 - 1276

Published: Feb. 7, 2024

A novel and highly selective electrochemical method for the synthesis of diverse quinazolinone oximes via direct electrooxidation primary amines/C(sp2)–H functionalization has been developed. The reaction is conducted in an undivided cell under constant current conditions oxidant-free, open-air, eco-friendly. Notably, protocol shows good functional group tolerance, providing versatile yields. Moreover, mechanism investigated through control experiments cyclic voltammogram (CV) experiments.

Language: Английский

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The efficient synthesis of three-membered rings via photo- and electrochemical strategies

Chemical Science, Journal Year: 2024, Volume and Issue: 15(34), P. 13576 - 13604

Published: Jan. 1, 2024

Three-membered rings, such as epoxides, aziridines, oxaziridines, cyclopropenes, vinyloxaziridines, and azirines, are recognized crucial pharmacophores building blocks in organic chemistry drug discovery. Despite the significant advances synthesis of these rings through photo/electrochemical methods over past decade, there has currently been no focused discussion updated overviews on this topic. Therefore, we presented review article efficient three-membered using photo- electrochemical strategies, covering literature since 2015. In study, a conceptual overview detailed discussions were provided to illustrate advancement field. Moreover, brief outlines current challenges opportunities synthesizing strategies.

Language: Английский

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Electrochemical Synthesis of Trisubstituted Oxazoles and Imines from β‐Diketones and Amines

ChemElectroChem, Journal Year: 2022, Volume and Issue: 9(15)

Published: June 13, 2022

Abstract An electrochemical oxidation reaction was developed for the synthesis of trisubstituted oxazoles and imines. The use external oxidant transition‐metal catalyst avoided in methodology. Various imines were obtained moderate to excellent yields. mechanism studies propose involves a radical process.

Language: Английский

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Electrochemical flow aziridination of unactivated alkenes

National Science Review, Journal Year: 2023, Volume and Issue: 10(10)

Published: July 3, 2023

ABSTRACT Aziridines derived from bioactive molecules may have unique pharmacological activities, making them useful in pharmacology (e.g. mitomycin C). Furthermore, the substitution of epoxide moiety epothilone B with aziridine, an analog epoxides, yielded a pronounced enhancement its anticancer efficacy. Thus, there is interest developing novel synthetic technologies to produce aziridines molecules. However, known methods usually require metal catalysts, stoichiometric oxidants and/or pre-functionalized amination reagents, causing difficulty application. A practical approach without catalyst and extra-oxidant for aziridination demand, yet challenging. Herein, we report electro-oxidative flow protocol that accomplishes oxidant-free natural products. This process achieved by oxidative sulfonamide/alkene cross-coupling, which sulfonamide alkene undergo simultaneous oxidation or oxidized preferentially. Further treatments cell lines demonstrated activities these aziridines, supporting potential this method drug discovery.

Language: Английский

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Visible Light Photoredox Aziridination of Chalcones

Asian Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 12(11)

Published: Aug. 24, 2023

Abstract The aziridination of chalcones with iminoiodinanes under photoredox conditions has been reported. reaction proceeds through nitrene radical anion intermediate generated from iminoiodinanes. trapping anions by afforded trans ‐aziridine products exclusively. scope the in terms both substrates is considerably wide and most cases ‐3‐aryl‐aziridine‐2‐ketones were isolated good yields. challenging due to electron‐deficient nature substrate, making this only second example (after trifluoromethyl alkenes) photocatalytic double bonds.

Language: Английский

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