Journal ArticleDOI
The Cope rearrangement in theoretical retrospect
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In this article, a critical review of the computational study of the Cope rearrangement of 1,5-hexadiene and its derivatives is presented and it is demonstrated that a realistic potential energy surface in the transition region can be obtained only at very high levels of approximation.Abstract:
This critical review highlights intricacies of the computational study of the Cope rearrangement of 1,5-hexadiene and its derivatives It is demonstrated that a realistic potential energy surface in the transition region can be obtained only at very high levels of approximation The emphasis is on the reasons why some generally reliable methods fail to make even qualitatively correct predictions about this reactionread more
Citations
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A Standard Set of Pericyclic Reactions of Hydrocarbons for the Benchmarking of Computational Methods: The Performance of ab Initio, Density Functional, CASSCF, CASPT2, and CBS-QB3 Methods for the Prediction of Activation Barriers, Reaction Energetics, and Transition State Geometries
Vildan Güner,Kelli S. Khuong,Andrew G. Leach,Patrick Lee,Michael D. Bartberger,Kendall N. Houk +5 more
TL;DR: In this article, experimental and theoretical data are provided for a set of 11 pericyclic reactions of unsaturated hydrocarbons, and experimental data are evaluated and standardized to ΔH⧧ 0K for comparison to theory.
Journal ArticleDOI
Singlet diradicals: from transition states to crystalline compounds.
David Scheschkewitz,Hideki Amii,Heinz Gornitzka,Wolfgang W. Schoeller,Didier Bourissou,Guy Bertrand,Guy Bertrand +6 more
TL;DR: The availability of diradicals that can be handled under standard laboratory conditions will lead to further insight into their chemical and physical properties, raising the likelihood of practical applications, especially in the field of molecular materials such as electrical conductors and ferromagnets.
Journal ArticleDOI
Palladium‐Catalyzed Asymmetric Allylic Alkylation of Cyclic Dienol Carbonates: Efficient Route to Enantioenriched γ‐Butenolides Bearing an All‐Carbon α‐Quaternary Stereogenic Center
TL;DR: Several methods for the enantioselective synthesis and transformation of the title compounds are presented in this paper, and several methods for their enanti-selective synthesis are described.
Journal ArticleDOI
Germacrenes A―E and related compounds: thermal, photochemical and acid induced transannular cyclizations
Journal ArticleDOI
Quantum theory of concerted electronic and nuclear fluxes associated with adiabatic intramolecular processes
Timm Bredtmann,D. J. Diestler,D. J. Diestler,Si-Dian Li,Jörn Manz,Jörn Manz,J. F. Pérez-Torres,Wen-Juan Tian,Yan-Bo Wu,Yonggang Yang,Hua-Jin Zhai +10 more
TL;DR: The quantum theory of concerted electronic and nuclear fluxes (CENFs) associated with electronically adiabatic intramolecular processes is presented and it is emphasized how the electronic continuity equation can be employed to circumvent the failure of the Born-Oppenheimer approximation.
References
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Journal ArticleDOI
Density‐functional thermochemistry. III. The role of exact exchange
TL;DR: In this article, a semi-empirical exchange correlation functional with local spin density, gradient, and exact exchange terms was proposed. But this functional performed significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.
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The importance of including dynamic electron correlation in ab initio calculations
Journal ArticleDOI
Quantum Mechanical Methods and the Interpretation and Prediction of Pericyclic Reaction Mechanisms
TL;DR: The computational study of pericyclic reactions, an important general class of organic reactions, now provides information about the transition structures of these processes with chemical accuracy, as judged by comparisons with experimental data, such as activation energies, substituent effects on rates, and kinetic isotope effects.
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