Synthesis of Isoxazole- And Oxazole-4-carboxylic Acids Derivatives by Controlled Isoxazole-Azirine-Isoxazole/Oxazole Isomerization

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Synthesis of Isoxazole- And Oxazole-4-carboxylic Acids Derivatives by Controlled Isoxazole-Azirine-Isoxazole/Oxazole Isomerization. / Serebryannikova, Anna V.; Galenko, Ekaterina E.; Novikov, Mikhail S.; Khlebnikov, Alexander F.

In: Journal of Organic Chemistry, Vol. 84, No. 23, 06.12.2019, p. 15567-15577.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{6bcab2a3456d4a3bb117a0933abcffa0,

title = "Synthesis of Isoxazole- And Oxazole-4-carboxylic Acids Derivatives by Controlled Isoxazole-Azirine-Isoxazole/Oxazole Isomerization",

abstract = "The first synthesis of isoxazole-4-carboxylic acid derivatives by domino isoxazole-isoxazole isomerization is reported. Fe(II)-catalyzed isomerization of 4-acyl-5-methoxy-/5-aminoisoxazoles (dioxane, 105 °C) leads to the formation of isoxazole-4-carboxylic esters and amides in good yields. 4-Formyl-5-methoxyisoxazoles give methyl oxazole-4-carboxylates under the same reaction conditions. Fe(II)-catalyzed isomerization of 4-acyl-5-methoxyisoxazoles under milder conditions (MeCN, 50 °C) allows the preparation of transient 2-acyl-2-(methoxycarbonyl)-2H-azirines. The azirines isomerize quantitatively either into isoxazoles under catalytic conditions (dioxane, 105 °C) or into oxazoles under noncatalytic thermolysis (o-dichlorobenzene, 170 °C). The mechanism of the isomerization and dependence of the reaction routes on substituents at starting isoxazole core and reaction conditions are discussed on the basis of DFT calculations.",

keywords = "NITRILE OXIDES, RING, REACTIVITY, CHLORIDES, OXAZOLES, PHOTOCHEMISTRY, CYCLOADDITION, CYCLIZATION, 2H-AZIRINES",

author = "Serebryannikova, {Anna V.} and Galenko, {Ekaterina E.} and Novikov, {Mikhail S.} and Khlebnikov, {Alexander F.}",

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

year = "2019",

month = dec,

day = "6",

doi = "10.1021/acs.joc.9b02536",

language = "English",

volume = "84",

pages = "15567--15577",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "23",

}

RIS

TY - JOUR

T1 - Synthesis of Isoxazole- And Oxazole-4-carboxylic Acids Derivatives by Controlled Isoxazole-Azirine-Isoxazole/Oxazole Isomerization

AU - Serebryannikova, Anna V.

AU - Galenko, Ekaterina E.

AU - Novikov, Mikhail S.

AU - Khlebnikov, Alexander F.

PY - 2019/12/6

Y1 - 2019/12/6

N2 - The first synthesis of isoxazole-4-carboxylic acid derivatives by domino isoxazole-isoxazole isomerization is reported. Fe(II)-catalyzed isomerization of 4-acyl-5-methoxy-/5-aminoisoxazoles (dioxane, 105 °C) leads to the formation of isoxazole-4-carboxylic esters and amides in good yields. 4-Formyl-5-methoxyisoxazoles give methyl oxazole-4-carboxylates under the same reaction conditions. Fe(II)-catalyzed isomerization of 4-acyl-5-methoxyisoxazoles under milder conditions (MeCN, 50 °C) allows the preparation of transient 2-acyl-2-(methoxycarbonyl)-2H-azirines. The azirines isomerize quantitatively either into isoxazoles under catalytic conditions (dioxane, 105 °C) or into oxazoles under noncatalytic thermolysis (o-dichlorobenzene, 170 °C). The mechanism of the isomerization and dependence of the reaction routes on substituents at starting isoxazole core and reaction conditions are discussed on the basis of DFT calculations.

AB - The first synthesis of isoxazole-4-carboxylic acid derivatives by domino isoxazole-isoxazole isomerization is reported. Fe(II)-catalyzed isomerization of 4-acyl-5-methoxy-/5-aminoisoxazoles (dioxane, 105 °C) leads to the formation of isoxazole-4-carboxylic esters and amides in good yields. 4-Formyl-5-methoxyisoxazoles give methyl oxazole-4-carboxylates under the same reaction conditions. Fe(II)-catalyzed isomerization of 4-acyl-5-methoxyisoxazoles under milder conditions (MeCN, 50 °C) allows the preparation of transient 2-acyl-2-(methoxycarbonyl)-2H-azirines. The azirines isomerize quantitatively either into isoxazoles under catalytic conditions (dioxane, 105 °C) or into oxazoles under noncatalytic thermolysis (o-dichlorobenzene, 170 °C). The mechanism of the isomerization and dependence of the reaction routes on substituents at starting isoxazole core and reaction conditions are discussed on the basis of DFT calculations.

KW - NITRILE OXIDES

KW - RING

KW - REACTIVITY

KW - CHLORIDES

KW - OXAZOLES

KW - PHOTOCHEMISTRY

KW - CYCLOADDITION

KW - CYCLIZATION

KW - 2H-AZIRINES

UR - http://www.scopus.com/inward/record.url?scp=85074763606&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/synthesis-isoxazole-oxazole4carboxylic-acids-derivatives-controlled-isoxazoleazirineisoxazoleoxazole

U2 - 10.1021/acs.joc.9b02536

DO - 10.1021/acs.joc.9b02536

M3 - Article

C2 - 31658810

AN - SCOPUS:85074763606

VL - 84

SP - 15567

EP - 15577

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 23

ER -

ID: 49487604