Amidyl radicals from N-(phenylthio)amides

Esker, John L.; Newcomb, Martin

doi:10.1016/s0040-4039(00)91819-7

Cited by 69 publications

(31 citation statements)

References 12 publications

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“…[16] The mechanism of this transformation has been investigated in detail. Although amide radicals have already been employed in cyclization reactions, [17] their involvement in the IBX-mediated reaction has been proven by a detailed analysis. [15b] It was concluded that the irreversible SET from the aryl moiety to the IBX´THF adduct is the rate-determining step of the reaction and can only proceed with a free ortho-position in the substrate as shown in the mesomeric structures A and B.…”

Section: Ibxðnew Reactions With An Old Reagentmentioning

confidence: 99%

IBX—New Reactions with an Old Reagent

Wirth

2001

Angew. Chem. Int. Ed.

205

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Section: Ibxðnew Reactions With An Old Reagentmentioning

confidence: 99%

IBX—New Reactions with an Old Reagent

Wirth

2001

Angew. Chem. Int. Ed.

205

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“…[12][13][14][15][16][17][18] As a result, amidyl radical formation was only achieved using strong oxidants (e.g., Dess-Martin periodinane, 15 iodoxybenzoic acid, 16 di-tert-butyl peroxide 17 ) at high temperatures (Scheme 1), [15][16][17][18] seriously compromising the applicability of the developed methods. Alternatively, the use of prefunctionalized amides [19][20][21] (e.g., LG = Cl, 22 SPh, 23 PTOC [pyridine-2-thione-Noxycarbonyl], 24 OAr, 25 or SO 2 Ar 26 ) made amidyl radicals more accessible under various conditions (i.e., UV light, radical initiators, reductants). However, this approach posed numerous disadvantages, such as the requirement for multi-step syntheses of the amide derivatives, poor stability of the functionalized amides, and the use of hazardous reagents, among others.…”

Section: Introductionmentioning

confidence: 99%

Merging Photoredox PCET with Ni-Catalyzed Cross-Coupling: Cascade Amidoarylation of Unactivated Olefins

Zheng

Gutiérrez‐Bonet

Molander

2019

Chem

110

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A rapid, highly diastereoselective amidoarylation of unactivated olefins was achieved to render medicinally privileged pyrrolidinone structures. Taking advantage of a photoredox proton-coupled electron transfer process, amidyl radicals were obtained from non-prefunctionalized N-H bonds under mild conditions, which were subsequently trapped by pendant olefins, delivering alkyl radicals for nickel-catalyzed cross-coupling. Mechanistic studies revealed the key balance between thermodynamically-driven radical generation and kineticallydriven cyclization, which led to expanding the scope toward urea and carbamate substrates.

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“…Іншим зручним реагентом для перебігу ра-дикальних циклізацій є Bu 3 SnH [69][70][71], під дією якого N-фенілсульфаніламід 133 в присутності ра-дикального ініціатора AIBN циклізується до від-повідного γ-лактаму 134 з високим виходом [70] (схема 55). Розроблений практичний одностадійний ме-тод синтезу нітровмісних лактамів 136 ферум-ка-талітичним хлоронітруванням амідів 135, що су-проводжується утворенням продуктів елімінуван-ням А та їх подальшою циклізацією [72] (схема 56).…”

Section: радикальні циклізаціїunclassified

Heterocyclization of amides of alkenylcarboxylic acids

Tsyzoryk¹,

Васькевич²,

Вовк³

2015

J. org. pharm. chem.

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(Ховейда, Граббса, Нолана), реакції мета-тезису, а також радикальних процесів у регіо-та стереоселективних циклізаціях амідів у м'яких умовах. Розглянуті синтетичні варіанти носять загальний характер і дозволяють поряд із процесами циклізації здійснювати спрямовану функціоналізацію O-, N-, S-вмісних малих та середніх гетероциклічних систем. HETEROCYCLIZATION OF AMIDES OF ALKENYLCARBOXYLIC ACIDS N.M.Tsyzoryk, A.I.Vaskevich, M.V.Vovk Key words: amides of alkenylcarboxylic acids; electrophilic intramolecular cyclization; lactones; lactams The latest published data on heterocyclization of amides of alkenylcarboxylic acids have been systematized. It has been proven that the electrophilic intramolecular cyclization reaction of functionally substituted olefins opened in the 70s of the last century is a convenient way of constructing different oxygen-, nitrogen-and sulfurcontaining heterocyclic compounds. It has been noted that anilides of unsaturated carboxylic acids as bifunctional nucleophilic systems containing alkenyl and aminocarbonyl functions are useful models to study the electrophilic cyclization reaction, which leads to formation of O-and N-containing heterocycles (lactones and lactams). The last of them belong to the important types of compounds used as key blocks in the synthesis of biologically active alkaloids and their analogues, pharmaceutical and agrochemical products. The effective approaches to the synthesis of new types of functionalized lactones and lactams have been developed; amides of 3-butenoic, 4-pentenoic and 5-hexenoic acids are often used as substrates for their design. Along with classical methods of synthesis of lactones and lactams the literary sources relating to the use of original catalytic electrophilic systems (Nolan, Grubbs, Hoveyda), the metathesis reaction and radical processes in regio-and stereoselective cyclization of amides under mild conditions have been analyzed and summarized in the article. The synthetic versions considered are general in nature and allow to perform the targeted functionalization of O-, N-, S-containing heterocyclic small and medium-sized systems along with the cyclization processes. ГЕТЕРОЦИКЛИЗАЦИИ АМИДОВ АЛКЕНИЛКАРБОНОВЫХ КИСЛОТ

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Amidyl radicals from N-(phenylthio)amides

Cited by 69 publications

References 12 publications

IBX—New Reactions with an Old Reagent

IBX—New Reactions with an Old Reagent

Merging Photoredox PCET with Ni-Catalyzed Cross-Coupling: Cascade Amidoarylation of Unactivated Olefins

Heterocyclization of amides of alkenylcarboxylic acids

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