Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Сен. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Язык: Английский

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Catalytic Synthesis of Cyclic Guanidines via Hydrogen Atom Transfer and Radical-Polar Crossover

ACS Catalysis, Год журнала: 2021, Номер 11(2), С. 900 - 906

Опубликована: Янв. 5, 2021

Cyclic guanidines are found in many biologically active compounds and natural products. Further, the formation of atypical seven-membered ring cyclic guanidine remains challenging because a lack efficient preparation strategies low yield. Herein, catalytic synthetic method for was developed via transition-metal hydrogen atom transfer radical-polar crossover. This mild functional-group-tolerant process enabled cyclization alkenyl bearing common protective groups, such as Cbz Boc groups. powerful provided not only typical five- six-membered rings but also ring. The derivatization products afforded various heterocycles. We investigated selective monoprotected or heteroprotected (TFA Boc) their further derivatizations.

Язык: Английский

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Convergent Palladium-Catalyzed Stereospecific Arginine Glycosylation Using Glycals

Organic Letters, Год журнала: 2021, Номер 23(10), С. 4008 - 4012

Опубликована: Май 12, 2021

A stereospecific convergent peptide arginine glycosylation method is reported for the first time. recently discovered invigorated interests of modification, which has been challenging, because inertness guanidino side chain. The approach renders glycoside construction convergently. Catalyzed by palladium complex, glycals modify groups in one step with high functional group tolerance at ambient temperature. glycosylated products may be converted to glycopeptide analogues few steps.

Язык: Английский

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Synthesis of Five-Membered Cyclic Guanidines via Cascade [3 + 2] Cycloaddition of α-Haloamides with Organo-cyanamides

The Journal of Organic Chemistry, Год журнала: 2021, Номер 86(4), С. 3546 - 3554

Опубликована: Фев. 4, 2021

The convenient preparation of N2-unprotected five-membered cyclic guanidines was achieved through a cascade [3 + 2] cycloaddition between organo-cyanamides and α-haloamides under mild conditions in good to excellent yields (up 99%). corresponding could be easily transformed into hydantoins via hydrolysis.

Язык: Английский

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Tandem Radical Fragmentation/Cyclization of Guanidinylated Monosaccharides Grants Access to Medium-Sized Polyhydroxylated Heterocycles

Organic Letters, Год журнала: 2020, Номер 22(21), С. 8492 - 8495

Опубликована: Окт. 19, 2020

The fragmentation of anomeric alkoxyl radicals (ARF) and the subsequent cyclization promoted by hypervalent iodine provide an excellent method for synthesis guanidino-sugars. methodology described herein is one few existing general methodologies formation medium-sized exo- endoguanidine-containing heterocycles presenting a high degree oxygenation in their structure.

Язык: Английский

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Direct synthesis of N₂-unprotected five-membered cyclic guanidines by regioselective [3 + 2] annulation of aziridines and cyanamides

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(6), С. 1574 - 1579

Опубликована: Янв. 1, 2022

This work disclosed the first direct synthesis of N 2 -unprotected five-membered cyclic guanidines via a regioselective ring-opening/5- exo-dig cyclization strategy between aziridines and cyanamides under mild conditions.

Язык: Английский

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N-Iodosuccinimide-Promoted [3 + 2] Annulation Reaction of Aryldiazonium Salts with Guanidines To Construct Aminotetrazoles

Organic Letters, Год журнала: 2021, Номер 23(22), С. 8894 - 8898

Опубликована: Ноя. 8, 2021

A N-iodosuccinimide (NIS)-promoted [3 + 2] annulation reaction of aryldiazonium salts with guanidines has been developed for the construction previously elusive 2-aryl-5-amino-2H-tetrazoles. This transformation takes advantage readily available starting materials, proceeds under metal-free, mild, and robust conditions, holds broad functional group compatibility. The utility this protocol is further manifested via coupling, annulation, deamination, denitrogenation derivatizations.

Язык: Английский

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A Review of the Synthetic Strategies toward Dihydropyrrolo[1,2-a]Pyrazinones

Organics, Год журнала: 2021, Номер 2(2), С. 118 - 141

Опубликована: Июнь 4, 2021

Dihydropyrrolo[1,2-a]pyrazinone rings are a class of heterocycles present in wide range bioactive natural products and analogues thereof. As direct result their bioactivity, the synthesis this privileged compounds has been extensively studied. This review provides an overview these synthetic pathways. The literature is covered up until 2020 organized according to specific strategies used construct scaffold: fusing pyrazinone existing pyrrole, employing pyrazinone-first strategy, array multicomponent reactions some miscellaneous reactions.

Язык: Английский

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Copper and In Situ-Generated Triflic Acid Relay-Promoted Four-Component Cascade Reaction for the Construction of Polysubstituted Cycloguanidines

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(13), С. 8400 - 8412

Опубликована: Июнь 23, 2023

An unprecedented copper and in situ-generated triflic acid relay-promoted four-component cascade reaction of cyanamides, diaryliodonium triflates, propargylic amines, H2O was established for rapid concise construction diverse five-membered cycloguanidines. Copper-catalyzed guanidination/intramolecular hydroamination HOTf-accelerated hydration proceeded sequentially with high level chemoselectivity regioselectivity, six new bonds were simultaneously built yields. Thus, triflates served not only as an arylation reagent but also internal promoter, establishing alternative strategy highly efficient utilization trifates.

Язык: Английский

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Copper(I)-Catalyzed α,β-Dehydrogenative [2 + 3] Heteroannulation of Saturated Amines with Diaziridinone via Hydrogen Atom Transfer

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 18107 - 18115

Опубликована: Ноя. 22, 2024

The site-selective functionalization of carbon(sp3)–hydrogen bonds in saturated amines remains a persistent challenge owing to their intrinsic electronic deficiency, particularly activating the α and β positions simultaneously for annulation reactions. Herein, we report copper(I)-catalyzed dehydrogenation [2 + 3] cycloaddition commercially available with diaziridinone, which facilitated direct synthesis highly valuable imidazolidone derivatives. Operationally simple methodology has broad substrate scope convenient scalability, providing an effective complementary platform rapid incorporation N-heterocycles into amine molecules. Furthermore, comprehensive mechanistic investigations computational studies indicated pathway radical-type hydrogen atom transfer cycloaddition, were promoted by four-membered copper(III) species.

Язык: Английский

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