Nature of the Nucleophilic Oxygenation Reagent Is Key to Acid-Free Gold-Catalyzed Conversion of Terminal and Internal Alkynes to 1,2-Dicarbonyls

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Nature of the Nucleophilic Oxygenation Reagent Is Key to Acid-Free Gold-Catalyzed Conversion of Terminal and Internal Alkynes to 1,2-Dicarbonyls. / Dubovtsev, Alexey Yu.; Shcherbakov, Nikolay V.; Dar'in, Dmitry V.; Kukushkin, Vadim Yu.

в: Journal of Organic Chemistry, Том 85, № 2, 17.01.2020, стр. 745-757.

Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование

BibTeX

@article{2e8ae81da425409c85bd0feed4c37a37,

title = "Nature of the Nucleophilic Oxygenation Reagent Is Key to Acid-Free Gold-Catalyzed Conversion of Terminal and Internal Alkynes to 1,2-Dicarbonyls",

abstract = "2,3-Dichloropyridine N-oxide, a novel oxygen transfer reagent, allows the conductance of the gold(I)-catalyzed oxidation of alkynes to 1,2-dicarbonyls in the absence of any acid additives and under mild conditions to furnish the target species, including those derivatized by highly acid-sensitive groups. The developed strategy is effective for a wide range of alkyne substrates such as terminal- and internal alkynes, ynamides, alkynyl ethers/thioethers, and even unsubstituted acetylene (40 examples; yields up to 99%). The oxidation was successfully integrated into the trapping of reactive dicarbonyls by one-pot heterocyclization and into the synthesis of six-membered azaheterocycles. This synthetic acid-free route was also successfully applied for the total synthesis of a natural 1,2-diketone.",

keywords = "ONE-POT SYNTHESIS, C BOND-CLEAVAGE, MOLECULAR-OXYGEN, OXIDATION, BENZIL, DERIVATIVES, PALLADIUM, EFFICIENT, 1,2-DIKETONES, CARBENES",

author = "Dubovtsev, {Alexey Yu.} and Shcherbakov, {Nikolay V.} and Dar'in, {Dmitry V.} and Kukushkin, {Vadim Yu.}",

note = "Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

year = "2020",

month = jan,

day = "17",

doi = "10.1021/acs.joc.9b02785",

language = "English",

volume = "85",

pages = "745--757",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "2",

}

RIS

TY - JOUR

T1 - Nature of the Nucleophilic Oxygenation Reagent Is Key to Acid-Free Gold-Catalyzed Conversion of Terminal and Internal Alkynes to 1,2-Dicarbonyls

AU - Dubovtsev, Alexey Yu.

AU - Shcherbakov, Nikolay V.

AU - Dar'in, Dmitry V.

AU - Kukushkin, Vadim Yu.

PY - 2020/1/17

Y1 - 2020/1/17

N2 - 2,3-Dichloropyridine N-oxide, a novel oxygen transfer reagent, allows the conductance of the gold(I)-catalyzed oxidation of alkynes to 1,2-dicarbonyls in the absence of any acid additives and under mild conditions to furnish the target species, including those derivatized by highly acid-sensitive groups. The developed strategy is effective for a wide range of alkyne substrates such as terminal- and internal alkynes, ynamides, alkynyl ethers/thioethers, and even unsubstituted acetylene (40 examples; yields up to 99%). The oxidation was successfully integrated into the trapping of reactive dicarbonyls by one-pot heterocyclization and into the synthesis of six-membered azaheterocycles. This synthetic acid-free route was also successfully applied for the total synthesis of a natural 1,2-diketone.

AB - 2,3-Dichloropyridine N-oxide, a novel oxygen transfer reagent, allows the conductance of the gold(I)-catalyzed oxidation of alkynes to 1,2-dicarbonyls in the absence of any acid additives and under mild conditions to furnish the target species, including those derivatized by highly acid-sensitive groups. The developed strategy is effective for a wide range of alkyne substrates such as terminal- and internal alkynes, ynamides, alkynyl ethers/thioethers, and even unsubstituted acetylene (40 examples; yields up to 99%). The oxidation was successfully integrated into the trapping of reactive dicarbonyls by one-pot heterocyclization and into the synthesis of six-membered azaheterocycles. This synthetic acid-free route was also successfully applied for the total synthesis of a natural 1,2-diketone.

KW - ONE-POT SYNTHESIS

KW - C BOND-CLEAVAGE

KW - MOLECULAR-OXYGEN

KW - OXIDATION

KW - BENZIL

KW - DERIVATIVES

KW - PALLADIUM

KW - EFFICIENT

KW - 1,2-DIKETONES

KW - CARBENES

UR - http://www.scopus.com/inward/record.url?scp=85078512735&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/ee8d60cc-b4f2-3100-87e6-6af6d67b333c/

U2 - 10.1021/acs.joc.9b02785

DO - 10.1021/acs.joc.9b02785

M3 - Article

C2 - 31849233

AN - SCOPUS:85078512735

VL - 85

SP - 745

EP - 757

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 2

ER -

ID: 51524130