Electronic factors influencing the activation barrier of the Diels-Alder reaction. An ab initio study

Bach, Robert D.; McDouall, Joseph J. W.; Schlegel, H. Bernhard; Wolber, Gregory J.

doi:10.1021/jo00273a029

Cited by 80 publications

(41 citation statements)

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“…These results reinforce our previous findings that 6-31G*//3-21G and higher theoretical levels correctly model IDFLDO VHOHFWLYLW\ LQ cycloaddition reactions with norbornenes [7]. As expected, estimated energy barriers vary with the computational level applied [17]. In contrast to these findings, there was found no significant difference between activation energies for the formation of exo,endo-4 and endo,exo-5 adducts.…”

Section: Resultssupporting

confidence: 89%

High-level Computational Study of the Site-, Facial- and Stereoselectivities for the Diels-Alder Reaction Between o-Benzoquinone and Norbornadiene

2000

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Ab initio and DFT quantum chemical calculations have been applied to a study of the Diels-Alder reaction of o-benzoquinone as diene and norbornadiene as dienophile. Transition states for the different reactions are located and activation energies estimated. The prefered exo-π-facial selectivity and exo,endo-stereoselectivity exhibited in this cycloaddition are readily predicted using RHF/3-21G or higher levels of calculations. Differences between experimentally observed results and calculations may be explained by the postulation of a second, nonconcerted biradical mechanism leading to formation of hetero Diels-Alder products.

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Section: Resultssupporting

confidence: 89%

High-level Computational Study of the Site-, Facial- and Stereoselectivities for the Diels-Alder Reaction Between o-Benzoquinone and Norbornadiene

2000

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“…The geometries of the transitions states are drawn in Figs. 1 h The activation energy of Diels-Alder reactions is known to be sensitive to electron correlation (1 1, [17][18][19]. Activation energies are dramatically overestimated at HF and underestimated at MP2.…”

Section: Methodsmentioning

confidence: 99%

Theoretical exammation of the Diels–Alder reaction of 1,3-butadiene with cyclopentadiene and 2H-phosphole

Bachrach¹,

Perriott²

1996

Can. J. Chem.

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All Diels-Alder reactions between 1,3-butadiene and cyclopentadiene or 2H-phosphole have been examined at the MP4SDQJ6-3 lG*//HF/6-31G* level. There is remarkable similarity between the two systems. The thermodynamic product is the bicyclo[4.2.0]nonadiene while the kinetic product is the norbornene product. There is a slight kinetic preference for the endo addition and for the butadiene to be in the s-trans conformation. Except for the case where butadiene is the diene component and addition is endo, the reactions are concerted and synchronous. In these other two cases, the reaction is stepwise with a diradical intermediate.Key words: phosphole, Diels-Alder reaction, topological electron density analysis.RCsumC : On a CtudiC toutes les rkactions de Diels-Alder entre le buta-1,3-dikne et le cyclopentadikne ou le 2H-phosphole au niveau MP4SDQJ6-3 lG*NHF/6-3 lG*. I1 existe une similarit6 remarquable entre les deux systkmes. Le produit thermodynamique est le bicyclo[4.2.0]nonadikne alors que le produit cinCtique est le produit norbornkne. I1 y a une 1Cgkre prCf6rence cinCtique en faveur de I'addition etldo et pour que le butadikne soit dans la conformation s-trans. A l'exception du cas ou le butadikne agit comme butadikne et que I'addition est endo, toutes les rCactions sont concertCes et synchrones. Dans ces deux autres cas, la rCaction se fait par Ctape avec un intermkdiaire diradicalaire.Mots clPs : phosphole, rCaction de Diels-Alder, analyse topologique de la densit6 Clectronique.[Traduit par la rCdaction]

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“…By comparing the free energy barriers and transition state heights of the two pathways with the undermentioned energies and barriers of the cascade radical cyclization and subsequent radical oxidations, one can readily draw a conclusion that the iodine-abstraction of 1 is more possible than the intramolecular cycloaddition-elimination. It has been widely known that a Diels-Alder addition reaction generally possesses a very high activation barrier [94][95][96][97][98][99][100] and the reductive removals of I and Br atoms from the compounds bearing vinyl-or alkyl-halogen bonds by Å SnMe 3 or Å SnBu 3 are very easy [101][102][103][104][105][106].…”

Section: Deiodination and Diels-alder Cycloaddition-elimination Channelsmentioning

confidence: 99%

Cascade cyclization of 1-(2-yl-3-phenylprop-2-enyl)-6-oxo-1,6-dihydropyridine-2-carbonitrile radical: Mechanistic insights from DFT study

Yuan

2014

Computational and Theoretical Chemistry

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Electronic factors influencing the activation barrier of the Diels-Alder reaction. An ab initio study

Cited by 80 publications

References 0 publications

High-level Computational Study of the Site-, Facial- and Stereoselectivities for the Diels-Alder Reaction Between o-Benzoquinone and Norbornadiene

High-level Computational Study of the Site-, Facial- and Stereoselectivities for the Diels-Alder Reaction Between o-Benzoquinone and Norbornadiene

Theoretical exammation of the Diels–Alder reaction of 1,3-butadiene with cyclopentadiene and 2H-phosphole

Cascade cyclization of 1-(2-yl-3-phenylprop-2-enyl)-6-oxo-1,6-dihydropyridine-2-carbonitrile radical: Mechanistic insights from DFT study

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