Effect of configuration of 2-vinyldiazocarbonyl compounds on their reactivity: Experimental and computational study

M.B. Supurgibekov, D. Cantillo, C.O. Kappe, G.K. Surya Prakash, V.A. Nikolaev

Research output

8 Citations (Scopus)

Abstract

Non-fluorinated vinyldiazo compounds with trans-configuration irrespective of the nature of 3-R1-substituent (R1 = H, Me, TBSO) even under ambient conditions easily cyclize to produce pyrazoles, while cis-stereoisomers undergo similar ring closure only at elevated temperatures or decompose to produce vinyloxocarbene reaction products. The 3-CF 3-substituted analogues with cis- or trans-configuration do not produce pyrazoles at all, but on heating furnish only vinylcarbene derived products. DFT calculations of theoretical energy barriers adequately explain the different experimental reactivity found for stereoisomeric vinyldiazocarbonyl compounds, and a new model for their interconversion through the corresponding pyrazoles has been suggested. © The Royal Society of Chemistry.
Original languageEnglish
Pages (from-to)682-689
JournalOrganic and Biomolecular Chemistry
Issue number4
DOIs
Publication statusPublished - 2014

Fingerprint

Pyrazoles
reactivity
configurations
reaction products
closures
Stereoisomerism
Energy barriers
chemistry
analogs
Reaction products
Discrete Fourier transforms
Heating
heating
rings
products
Temperature
temperature
energy

Cite this

Supurgibekov, M.B. ; Cantillo, D. ; Kappe, C.O. ; Surya Prakash, G.K. ; Nikolaev, V.A. / Effect of configuration of 2-vinyldiazocarbonyl compounds on their reactivity: Experimental and computational study. In: Organic and Biomolecular Chemistry. 2014 ; No. 4. pp. 682-689.
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Effect of configuration of 2-vinyldiazocarbonyl compounds on their reactivity: Experimental and computational study. / Supurgibekov, M.B.; Cantillo, D.; Kappe, C.O.; Surya Prakash, G.K.; Nikolaev, V.A.

In: Organic and Biomolecular Chemistry, No. 4, 2014, p. 682-689.

Research output

TY - JOUR

T1 - Effect of configuration of 2-vinyldiazocarbonyl compounds on their reactivity: Experimental and computational study

AU - Supurgibekov, M.B.

AU - Cantillo, D.

AU - Kappe, C.O.

AU - Surya Prakash, G.K.

AU - Nikolaev, V.A.

PY - 2014

Y1 - 2014

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AB - Non-fluorinated vinyldiazo compounds with trans-configuration irrespective of the nature of 3-R1-substituent (R1 = H, Me, TBSO) even under ambient conditions easily cyclize to produce pyrazoles, while cis-stereoisomers undergo similar ring closure only at elevated temperatures or decompose to produce vinyloxocarbene reaction products. The 3-CF 3-substituted analogues with cis- or trans-configuration do not produce pyrazoles at all, but on heating furnish only vinylcarbene derived products. DFT calculations of theoretical energy barriers adequately explain the different experimental reactivity found for stereoisomeric vinyldiazocarbonyl compounds, and a new model for their interconversion through the corresponding pyrazoles has been suggested. © The Royal Society of Chemistry.

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DO - 10.1039/c3ob42102c

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JO - Organic and Biomolecular Chemistry

JF - Organic and Biomolecular Chemistry

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