Synthesis of 1-(2-Aminovinyl)indoles and 1,3′-Biindoles by Reaction of 2,2-Diaryl-Substituted 2 H-Azirines with α-Imino Rh(II) Carbenoids

Adel R. Khaidarov, Nikolai V. Rostovskii, Andrey A. Zolotarev, Alexander F. Khlebnikov, Mikhail S. Novikov

Research output

4 Citations (Scopus)

Abstract

An effective and operationally simple method for the preparation of 1-(2-(sulfonamido)vinyl)indoles (SAV-indoles) by the Rh(II)-catalyzed reaction of 2,2-diaryl-2H-azirines with 1-sulfonyl-1,2,3-triazoles has been developed. This method enables the stereoselective synthesis of a variety of 1,2,3-trisubstituted indoles having a Z configuration of the (1-aryl-2-(sulfonamido)vinyl) substituent. The reaction mechanism, supported by DFT calculations, involves the formation of 1,4-diazahexa-1,3,5-trienes, which rapidly cyclize to 2,2-diaryl-1-sulfonyl-1,2-dihydropyrazines. These compounds can be isolated at an early stage of the reaction, but under prolonged heating they isomerize into 7aH-indolium ylides, followed by a barrierless 1,5-prototropic shift to SAV-indoles. The developed methodology was also applied to the preparation of 1,3′-biindoles from 2,2-diaryl-2H-azirines using 3-diazoindolin-2-imines instead of 1-sulfonyl-1,2,3-triazoles.

Original languageEnglish
Pages (from-to)3743-3753
Number of pages11
JournalJournal of Organic Chemistry
DOIs
Publication statusPublished - 1 Jan 2019

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Azirines
Indoles
Imines
Discrete Fourier transforms
Heating
1-sulfonyl-1,2,3-triazole

Scopus subject areas

  • Organic Chemistry

Cite this

@article{2d7ae76cd36b4eafb74da36b745a0064,
title = "Synthesis of 1-(2-Aminovinyl)indoles and 1,3′-Biindoles by Reaction of 2,2-Diaryl-Substituted 2 H-Azirines with α-Imino Rh(II) Carbenoids",
abstract = "An effective and operationally simple method for the preparation of 1-(2-(sulfonamido)vinyl)indoles (SAV-indoles) by the Rh(II)-catalyzed reaction of 2,2-diaryl-2H-azirines with 1-sulfonyl-1,2,3-triazoles has been developed. This method enables the stereoselective synthesis of a variety of 1,2,3-trisubstituted indoles having a Z configuration of the (1-aryl-2-(sulfonamido)vinyl) substituent. The reaction mechanism, supported by DFT calculations, involves the formation of 1,4-diazahexa-1,3,5-trienes, which rapidly cyclize to 2,2-diaryl-1-sulfonyl-1,2-dihydropyrazines. These compounds can be isolated at an early stage of the reaction, but under prolonged heating they isomerize into 7aH-indolium ylides, followed by a barrierless 1,5-prototropic shift to SAV-indoles. The developed methodology was also applied to the preparation of 1,3′-biindoles from 2,2-diaryl-2H-azirines using 3-diazoindolin-2-imines instead of 1-sulfonyl-1,2,3-triazoles.",
author = "Khaidarov, {Adel R.} and Rostovskii, {Nikolai V.} and Zolotarev, {Andrey A.} and Khlebnikov, {Alexander F.} and Novikov, {Mikhail S.}",
year = "2019",
month = "1",
day = "1",
doi = "10.1021/acs.joc.8b03205",
language = "English",
pages = "3743--3753",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",

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T1 - Synthesis of 1-(2-Aminovinyl)indoles and 1,3′-Biindoles by Reaction of 2,2-Diaryl-Substituted 2 H-Azirines with α-Imino Rh(II) Carbenoids

AU - Khaidarov, Adel R.

AU - Rostovskii, Nikolai V.

AU - Zolotarev, Andrey A.

AU - Khlebnikov, Alexander F.

AU - Novikov, Mikhail S.

PY - 2019/1/1

Y1 - 2019/1/1

N2 - An effective and operationally simple method for the preparation of 1-(2-(sulfonamido)vinyl)indoles (SAV-indoles) by the Rh(II)-catalyzed reaction of 2,2-diaryl-2H-azirines with 1-sulfonyl-1,2,3-triazoles has been developed. This method enables the stereoselective synthesis of a variety of 1,2,3-trisubstituted indoles having a Z configuration of the (1-aryl-2-(sulfonamido)vinyl) substituent. The reaction mechanism, supported by DFT calculations, involves the formation of 1,4-diazahexa-1,3,5-trienes, which rapidly cyclize to 2,2-diaryl-1-sulfonyl-1,2-dihydropyrazines. These compounds can be isolated at an early stage of the reaction, but under prolonged heating they isomerize into 7aH-indolium ylides, followed by a barrierless 1,5-prototropic shift to SAV-indoles. The developed methodology was also applied to the preparation of 1,3′-biindoles from 2,2-diaryl-2H-azirines using 3-diazoindolin-2-imines instead of 1-sulfonyl-1,2,3-triazoles.

AB - An effective and operationally simple method for the preparation of 1-(2-(sulfonamido)vinyl)indoles (SAV-indoles) by the Rh(II)-catalyzed reaction of 2,2-diaryl-2H-azirines with 1-sulfonyl-1,2,3-triazoles has been developed. This method enables the stereoselective synthesis of a variety of 1,2,3-trisubstituted indoles having a Z configuration of the (1-aryl-2-(sulfonamido)vinyl) substituent. The reaction mechanism, supported by DFT calculations, involves the formation of 1,4-diazahexa-1,3,5-trienes, which rapidly cyclize to 2,2-diaryl-1-sulfonyl-1,2-dihydropyrazines. These compounds can be isolated at an early stage of the reaction, but under prolonged heating they isomerize into 7aH-indolium ylides, followed by a barrierless 1,5-prototropic shift to SAV-indoles. The developed methodology was also applied to the preparation of 1,3′-biindoles from 2,2-diaryl-2H-azirines using 3-diazoindolin-2-imines instead of 1-sulfonyl-1,2,3-triazoles.

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