Synchronous or Asynchronous? An “Experimental” Transition State from a Direct Comparison of Experimental and Theoretical Kinetic Isotope Effects for a Diels−Alder Reaction

Beno, Brett R.; Houk, K. N.; Singleton, Daniel A.

doi:10.1021/ja9615278

Cited by 161 publications

(112 citation statements)

References 48 publications

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“…High-level computational studies in combination with kinetic isotope effect studies provide good evidence that for simple hydrocarbon systems, the aromatic stabilization of the transition states prevails in the neutral reaction. [20] The neutral reaction thus undergoes a concerted reaction that has an aromatic transition state.…”

Section: Aromaticity Of Transition Statesmentioning

confidence: 99%

Structure and Reactivity of Radical Ions: New Twists on Old Concepts

Donoghue¹,

Wiest²

2006

Chemistry A European J

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Electron transfer is the simplest reaction possible, yet it has a profound impact on the structure and reactivity of organic compounds. These changes allow a new look at some of the fundamental concepts that are used to explain organic chemistry, such as symmetry, aromaticity, and bonding. The results from high-level electronic structure calculations are used to analyze the mechanistic differences in the pericyclic reactions of simple hydrocarbons and their radical cation counterparts. The importance of state symmetry correlation, Jahn-Teller distortions, delocalization, and fractional bonding for the reaction pathways of hydrocarbon radical cations is discussed.

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Section: Aromaticity Of Transition Statesmentioning

confidence: 99%

Structure and Reactivity of Radical Ions: New Twists on Old Concepts

Donoghue¹,

Wiest²

2006

Chemistry A European J

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“…The combination of experimental and theoretical KIEs has recently proven to be a very successful method for the elucidation of reaction mechanisms. 19,[28][29][30][31][32][33] To apply this technique for the RuO 4 -catalyzed oxidation of alkanes, we computed the oxidation of selected alkanes for which experimental KIE data are available in the literature. 9,10 Knowledge of the structures and relative energies of possible transition states has shown to be helpful in pointing the way to the correct mechanism.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium Tetraoxide Oxidations of Alkanes: DFT Calculations of Barrier Heights and Kinetic Isotope Effects

Drees

Straßner

2005

J. Org. Chem.

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The oxidation of C-H and C-C bonds by metal-oxo compounds is of general interest. We studied the RuO4-mediated catalytic oxidation of several cycloalkanes such as adamantane and cis- and trans-decalin as well as methane. B3LYP/6-31G(d) calculations on the experimentally proposed (3+2) mechanism are in good agreement with known experimental results. Comparison of experimental and theoretical kinetic isotope effects confirms the proposed mechanism. Besides RuO4, we also looked at RuO4(OH)- as a potential active species to account for ruthenium tetraoxide oxidations under strong basic conditions.

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“…[25] The method also gives excellent geometries for transition structures of pericyclic reactions as shown by comparison of predicted kinetic isotope effects to high-precision experimental results. [26] Computational methodology: All calculations were performed with Gaussian 94 at the Becke3LYP/6-31G* level. [27,28] All geometries were fully optimized.…”

mentioning

confidence: 99%

Pressure-Induced Cycloadditions of Dicyanoacetylene to Strained Arenes: The Formation of Cyclooctatetraene, 9,10-Dihydronaphthalene, and Azulene Derivatives; A Degenerate [1,5] Sigmatropic Shift—Comparison between Theory and Experiment

et al. 1999

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Abstract:The reaction of dicyanoacetylene (DCA) with the partially hydrogenated dimethano-bridged anthracene and pentacene derivatives 3 and 18 lead to the (1:1) Diels ± Alder adducts 5 and 19, respectively, and to the 9,10-dihydronaphthalene derivatives 6 and 21, respectively. These compounds are intensely colored, most likely due to a charge-transfer absorption. Photolysis of the (1:1) adducts 5 and 19 produces the corresponding cyclooctatetraene derivatives 7 and 8, which are not planar despite the torsional constraints caused by the fusion of the eight-membered ring to norbornane and norbornene units. The mechanisms of formation of the dihydronaphthalene derivatives 6 and 21 were elucidated by the use of high pressure; this allowed the (2:1) adducts 11 and 20 to be detected as intermediates in the reaction of DCA with 5 or 19 to give 6 and 21, respectively. A degenerate rearrangement consisting formally of a [1,5] The finding that the irreversible rearrangement of 6 accompanied by the elimination of HCN to give the azulene derivative 14 proceeds only on heating of 6 to 80 8C in a polar solvent is good evidence for a polar mechanism in this case.

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Synchronous or Asynchronous? An “Experimental” Transition State from a Direct Comparison of Experimental and Theoretical Kinetic Isotope Effects for a Diels−Alder Reaction

Cited by 161 publications

References 48 publications

Structure and Reactivity of Radical Ions: New Twists on Old Concepts

Structure and Reactivity of Radical Ions: New Twists on Old Concepts

Ruthenium Tetraoxide Oxidations of Alkanes: DFT Calculations of Barrier Heights and Kinetic Isotope Effects

Pressure-Induced Cycloadditions of Dicyanoacetylene to Strained Arenes: The Formation of Cyclooctatetraene, 9,10-Dihydronaphthalene, and Azulene Derivatives; A Degenerate [1,5] Sigmatropic Shift—Comparison between Theory and Experiment

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