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

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

In: Journal of Organic Chemistry, Vol. 84, No. 7, 05.04.2019, p. 3743-3753.

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

BibTeX

@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.",

keywords = "CATALYZED 3+2 CYCLOADDITION, N-SULFONYL AZIDES, REGIOSELECTIVE SYNTHESIS, EFFICIENT SYNTHESIS, TERMINAL ALKYNES, INDOLES, 1-SULFONYL-1,2,3-TRIAZOLES, 3-DIAZOINDOLIN-2-IMINES, TRANSANNULATION, N-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 = apr,

day = "5",

doi = "10.1021/acs.joc.8b03205",

language = "English",

volume = "84",

pages = "3743--3753",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "7",

}

RIS

TY - JOUR

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 - 2019/4/5

Y1 - 2019/4/5

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.

KW - CATALYZED 3+2 CYCLOADDITION

KW - N-SULFONYL AZIDES

KW - REGIOSELECTIVE SYNTHESIS

KW - EFFICIENT SYNTHESIS

KW - TERMINAL ALKYNES

KW - INDOLES

KW - 1-SULFONYL-1,2,3-TRIAZOLES

KW - 3-DIAZOINDOLIN-2-IMINES

KW - TRANSANNULATION

KW - N-SULFONYL-1,2,3-TRIAZOLES

UR - http://www.scopus.com/inward/record.url?scp=85061274166&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/synthesis-12aminovinylindoles-13biindoles-reaction-22diarylsubstituted-2-hazirines-%CE%B1imino-rhii-carbe

U2 - 10.1021/acs.joc.8b03205

DO - 10.1021/acs.joc.8b03205

M3 - Article

AN - SCOPUS:85061274166

VL - 84

SP - 3743

EP - 3753

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 7

ER -

ID: 39753220