An Isoxazole Strategy for the Synthesis of α-Aminopyrrole Derivatives

Research outputpeer-review

Abstract

A synthesis of methyl 5-aminopyrrole-3-carboxylates from 4-methyleneisoxazol-3-ones via “cyanide Michael addition/methylation/reductive isoxazole-pyrrole transformation” is developed. The last step occurs in a domino mode involving Mo(CO)6-mediated reductive isoxazole ring-opening, Mo(CO)6-catalyzed cis-trans-isomerization of the enamine intermediate followed by 1,5-exo-dig cyclization. 5-Amino-1H-pyrrolo-3-carboxylates react with 1,3-diketones, affording pyrrolo[1,2-a]pyrimidine-7-carboxylates, and are easily converted into 2-diazo-2H-pyrrole-4-carboxylates. These compounds demonstrate the reactivity of both diazo compounds, giving pyrrole-containing products of intra/intermolecular azo coupling, and carbenes to give pyrrole-containing insertion products into CH and OH bonds under photolysis.
Original languageEnglish
JournalThe Journal of organic chemistry
DOIs
Publication statusE-pub ahead of print - 6 Aug 2019

Cite this

@article{6999b1ec14b3428aabf2f6120c7a1dcb,
title = "An Isoxazole Strategy for the Synthesis of α-Aminopyrrole Derivatives",
abstract = "A synthesis of methyl 5-aminopyrrole-3-carboxylates from 4-methyleneisoxazol-3-ones via “cyanide Michael addition/methylation/reductive isoxazole-pyrrole transformation” is developed. The last step occurs in a domino mode involving Mo(CO)6-mediated reductive isoxazole ring-opening, Mo(CO)6-catalyzed cis-trans-isomerization of the enamine intermediate followed by 1,5-exo-dig cyclization. 5-Amino-1H-pyrrolo-3-carboxylates react with 1,3-diketones, affording pyrrolo[1,2-a]pyrimidine-7-carboxylates, and are easily converted into 2-diazo-2H-pyrrole-4-carboxylates. These compounds demonstrate the reactivity of both diazo compounds, giving pyrrole-containing products of intra/intermolecular azo coupling, and carbenes to give pyrrole-containing insertion products into CH and OH bonds under photolysis.",
author = "Galenko, {Ekaterina E.} and Linnik, {Stanislav A.} and Khoroshilova, {Olesya V.} and Novikov, {Mikhail Sergeevich} and Khlebnikov, {Alexander F.}",
year = "2019",
month = "8",
day = "6",
doi = "10.1021/acs.joc.9b01634",
language = "English",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",

}

TY - JOUR

T1 - An Isoxazole Strategy for the Synthesis of α-Aminopyrrole Derivatives

AU - Galenko, Ekaterina E.

AU - Linnik, Stanislav A.

AU - Khoroshilova, Olesya V.

AU - Novikov, Mikhail Sergeevich

AU - Khlebnikov, Alexander F.

PY - 2019/8/6

Y1 - 2019/8/6

N2 - A synthesis of methyl 5-aminopyrrole-3-carboxylates from 4-methyleneisoxazol-3-ones via “cyanide Michael addition/methylation/reductive isoxazole-pyrrole transformation” is developed. The last step occurs in a domino mode involving Mo(CO)6-mediated reductive isoxazole ring-opening, Mo(CO)6-catalyzed cis-trans-isomerization of the enamine intermediate followed by 1,5-exo-dig cyclization. 5-Amino-1H-pyrrolo-3-carboxylates react with 1,3-diketones, affording pyrrolo[1,2-a]pyrimidine-7-carboxylates, and are easily converted into 2-diazo-2H-pyrrole-4-carboxylates. These compounds demonstrate the reactivity of both diazo compounds, giving pyrrole-containing products of intra/intermolecular azo coupling, and carbenes to give pyrrole-containing insertion products into CH and OH bonds under photolysis.

AB - A synthesis of methyl 5-aminopyrrole-3-carboxylates from 4-methyleneisoxazol-3-ones via “cyanide Michael addition/methylation/reductive isoxazole-pyrrole transformation” is developed. The last step occurs in a domino mode involving Mo(CO)6-mediated reductive isoxazole ring-opening, Mo(CO)6-catalyzed cis-trans-isomerization of the enamine intermediate followed by 1,5-exo-dig cyclization. 5-Amino-1H-pyrrolo-3-carboxylates react with 1,3-diketones, affording pyrrolo[1,2-a]pyrimidine-7-carboxylates, and are easily converted into 2-diazo-2H-pyrrole-4-carboxylates. These compounds demonstrate the reactivity of both diazo compounds, giving pyrrole-containing products of intra/intermolecular azo coupling, and carbenes to give pyrrole-containing insertion products into CH and OH bonds under photolysis.

UR - http://www.mendeley.com/research/isoxazole-strategy-synthesis-%CE%B1aminopyrrole-derivatives

UR - https://pubs.acs.org/doi/10.1021/acs.joc.9b01634

U2 - 10.1021/acs.joc.9b01634

DO - 10.1021/acs.joc.9b01634

M3 - Article

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

ER -