Rh(II)-Catalyzed Ring Expansion of Pyrazoles with Diazocarbonyl Compounds as a Method for the Preparation of 1,2-Dihydropyrimidines

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Rh(II)-Catalyzed Ring Expansion of Pyrazoles with Diazocarbonyl Compounds as a Method for the Preparation of 1,2-Dihydropyrimidines. / Koronatov, Alexander N.; Rostovskii, Nikolai V.; Khlebnikov, Alexander F.; Novikov, Mikhail Sergeevich.

In: Journal of Organic Chemistry, Vol. 83, No. 16, 17.08.2018, p. 9210–9219.

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

BibTeX

@article{07eaaf11903c4d2ba01434c22fde8346,

title = "Rh(II)-Catalyzed Ring Expansion of Pyrazoles with Diazocarbonyl Compounds as a Method for the Preparation of 1,2-Dihydropyrimidines",

abstract = "High yield synthesis of 1,2-dihydropyrimidines by Rh(II)-catalyzed reaction of diazocarbonyl compounds with 1,4-di- and 1,4,5-trisubstituted pyrazoles is reported. This reaction represents the first example of a carbenoid insertion into an N-N bond and provides a novel approach to 4-unsubstituted 1,2-dihydropyrimidines with a broad range of functional group tolerance. According to DFT calculations the pyrazole ring expansion proceeds via the sequential formation of the metal-bound pyrazolium ylide, metal-free pyrazolium ylide and 1,5-diazahexatriene followed by 1,6-cyclization.",

keywords = "C-H BONDS, ONE-POT SYNTHESIS, DIAZO-COMPOUNDS, 3+2 CYCLOADDITION, BUILDING-BLOCKS, N-YLIDES, DERIVATIVES, ISOXAZOLES, PYRIDINIUM, REARRANGEMENT",

author = "Koronatov, {Alexander N.} and Rostovskii, {Nikolai V.} and Khlebnikov, {Alexander F.} and Novikov, {Mikhail Sergeevich}",

year = "2018",

month = aug,

day = "17",

doi = "10.1021/acs.joc.8b01228",

language = "English",

volume = "83",

pages = " 9210–9219",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "16",

}

RIS

TY - JOUR

T1 - Rh(II)-Catalyzed Ring Expansion of Pyrazoles with Diazocarbonyl Compounds as a Method for the Preparation of 1,2-Dihydropyrimidines

AU - Koronatov, Alexander N.

AU - Rostovskii, Nikolai V.

AU - Khlebnikov, Alexander F.

AU - Novikov, Mikhail Sergeevich

PY - 2018/8/17

Y1 - 2018/8/17

N2 - High yield synthesis of 1,2-dihydropyrimidines by Rh(II)-catalyzed reaction of diazocarbonyl compounds with 1,4-di- and 1,4,5-trisubstituted pyrazoles is reported. This reaction represents the first example of a carbenoid insertion into an N-N bond and provides a novel approach to 4-unsubstituted 1,2-dihydropyrimidines with a broad range of functional group tolerance. According to DFT calculations the pyrazole ring expansion proceeds via the sequential formation of the metal-bound pyrazolium ylide, metal-free pyrazolium ylide and 1,5-diazahexatriene followed by 1,6-cyclization.

AB - High yield synthesis of 1,2-dihydropyrimidines by Rh(II)-catalyzed reaction of diazocarbonyl compounds with 1,4-di- and 1,4,5-trisubstituted pyrazoles is reported. This reaction represents the first example of a carbenoid insertion into an N-N bond and provides a novel approach to 4-unsubstituted 1,2-dihydropyrimidines with a broad range of functional group tolerance. According to DFT calculations the pyrazole ring expansion proceeds via the sequential formation of the metal-bound pyrazolium ylide, metal-free pyrazolium ylide and 1,5-diazahexatriene followed by 1,6-cyclization.

KW - C-H BONDS

KW - ONE-POT SYNTHESIS

KW - DIAZO-COMPOUNDS

KW - 3+2 CYCLOADDITION

KW - BUILDING-BLOCKS

KW - N-YLIDES

KW - DERIVATIVES

KW - ISOXAZOLES

KW - PYRIDINIUM

KW - REARRANGEMENT

UR - http://www.scopus.com/inward/record.url?scp=85048874772&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/rhiicatalyzed-ring-expansion-pyrazoles-diazocarbonyl-compounds-method-preparation-12dihydropyrimidin

U2 - 10.1021/acs.joc.8b01228

DO - 10.1021/acs.joc.8b01228

M3 - Article

AN - SCOPUS:85048874772

VL - 83

SP - 9210

EP - 9219

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 16

ER -

ID: 28801780