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Experimental and theoretical studies of Diels-Alder reaction between methyl (Z)-2-nitro-3-(4-nitrophenyl)-2-propenoate and cyclopentadiene.

Jasiński R, Kwiatkowska M, Sharnin V, Barański A - Monatsh. Chem. (2013)

Bottom Line: The Diels-Alder reaction between methyl (Z)-2-nitro-3-(4-nitrophenyl)-2-propenoate and cyclopentadiene yields a mixture of carbodiene Diels-Alder adducts.B3LYP/6-31G(d) simulations indicate that the conversion of addends into methyl (1R*,2S*,3S*,4R*)-2-nitro-3-(4-nitrophenyl)-bicyclo[2.2.1]hept-5-ene-2-carboxylate occurs via two-stage heterodiene Diels-Alder reaction and (in a second step) skeleton rearrangement of the primary cycloadduct, whereas the reaction leading to methyl (1R*,2R*,3R*,4R*)-2-nitro-3-(4-nitrophenyl)-bicyclo[2.2.1]hept-5-ene-2-carboxylate is a single-step process.

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Affiliation: Institute of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, Poland.

ABSTRACT

Abstract: The Diels-Alder reaction between methyl (Z)-2-nitro-3-(4-nitrophenyl)-2-propenoate and cyclopentadiene yields a mixture of carbodiene Diels-Alder adducts. B3LYP/6-31G(d) simulations indicate that the conversion of addends into methyl (1R*,2S*,3S*,4R*)-2-nitro-3-(4-nitrophenyl)-bicyclo[2.2.1]hept-5-ene-2-carboxylate occurs via two-stage heterodiene Diels-Alder reaction and (in a second step) skeleton rearrangement of the primary cycloadduct, whereas the reaction leading to methyl (1R*,2R*,3R*,4R*)-2-nitro-3-(4-nitrophenyl)-bicyclo[2.2.1]hept-5-ene-2-carboxylate is a single-step process.

No MeSH data available.


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Mentions: B3LYP/6–31G(d) calculations prove that the energy profiles of reactions leading finally to CDA products in the gas phase vary. For the pathway leading to 3 (see Table 1, Fig. 2 and Scheme 2) two transition states occur between the minima of reactants 1 + 2 and product 3. Whereas only one transition state occurs on the pathway leading to 4. Our attempts to find a pathway leading directly to bicycloheptene 3 were unsuccessful.


Experimental and theoretical studies of Diels-Alder reaction between methyl (Z)-2-nitro-3-(4-nitrophenyl)-2-propenoate and cyclopentadiene.

Jasiński R, Kwiatkowska M, Sharnin V, Barański A - Monatsh. Chem. (2013)

© Copyright Policy - OpenAccess
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC4495048&req=5

Mentions: B3LYP/6–31G(d) calculations prove that the energy profiles of reactions leading finally to CDA products in the gas phase vary. For the pathway leading to 3 (see Table 1, Fig. 2 and Scheme 2) two transition states occur between the minima of reactants 1 + 2 and product 3. Whereas only one transition state occurs on the pathway leading to 4. Our attempts to find a pathway leading directly to bicycloheptene 3 were unsuccessful.

Bottom Line: The Diels-Alder reaction between methyl (Z)-2-nitro-3-(4-nitrophenyl)-2-propenoate and cyclopentadiene yields a mixture of carbodiene Diels-Alder adducts.B3LYP/6-31G(d) simulations indicate that the conversion of addends into methyl (1R*,2S*,3S*,4R*)-2-nitro-3-(4-nitrophenyl)-bicyclo[2.2.1]hept-5-ene-2-carboxylate occurs via two-stage heterodiene Diels-Alder reaction and (in a second step) skeleton rearrangement of the primary cycloadduct, whereas the reaction leading to methyl (1R*,2R*,3R*,4R*)-2-nitro-3-(4-nitrophenyl)-bicyclo[2.2.1]hept-5-ene-2-carboxylate is a single-step process.

View Article: PubMed Central - PubMed

Affiliation: Institute of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, Poland.

ABSTRACT

Abstract: The Diels-Alder reaction between methyl (Z)-2-nitro-3-(4-nitrophenyl)-2-propenoate and cyclopentadiene yields a mixture of carbodiene Diels-Alder adducts. B3LYP/6-31G(d) simulations indicate that the conversion of addends into methyl (1R*,2S*,3S*,4R*)-2-nitro-3-(4-nitrophenyl)-bicyclo[2.2.1]hept-5-ene-2-carboxylate occurs via two-stage heterodiene Diels-Alder reaction and (in a second step) skeleton rearrangement of the primary cycloadduct, whereas the reaction leading to methyl (1R*,2R*,3R*,4R*)-2-nitro-3-(4-nitrophenyl)-bicyclo[2.2.1]hept-5-ene-2-carboxylate is a single-step process.

No MeSH data available.