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- W2090759554 abstract "The molecular mechanism of the α-chlorocyclobutanone transposition to yield cyclopropanecarboxylic acid, as a model of the Favorskii rearrangement, has been theoretically characterized in vacuo by means of ab initio molecular orbital procedures at the Hartree−Fock (HF) level of theory with the 6-31G* and 6-31+G* basis sets. The electron correlation has been estimated at the MP2/6-31G* level and calculations based on density functional theory, BLYP/6-31G*. The solvent effects are included at HF/6-31G* level by means of a polarizable continuum model. The questions related to the two accepted molecular mechanisms, the semibenzilic acid and the cyclopropanone transpositions, as well as the competition between both reaction pathways are addressed in this investigation. The dependence of the geometries of the stationary structures along the corresponding reaction pathways and the transition vectors associated with the transition structures upon theoretical methods is discussed. The analysis of the results shows that the electrostatic solute−solvent interactions modify appreciably the topology of the potential energy surface. The cyclopropanone mechanism is stabilized with respect to the semibenzilic acid mechanism, but this latter remains the energetically favorable reactive channel both in vacuo and in solution. The semibenzilic acid mechanism is a two-step process and the rate-limiting step corresponds to the nucleophilic attack of the hydroxyl ion on the carbon atom of the carbonyl group belonging to the α-chlorocyclobutanone ring. In the cyclopropanone mechanism three transition structures appear along the energy profile and the rate-limiting step is the dehydration process of the bicyclo[1.1.0]2-butanone intermediate with concomitant ring contraction and formation of the cyclopropanecarboxylic acid product." @default.
- W2090759554 created "2016-06-24" @default.
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- W2090759554 date "1997-02-01" @default.
- W2090759554 modified "2023-10-16" @default.
- W2090759554 title "A Theoretical Study of the Favorskii Rearrangement. Calculation of Gas-Phase Reaction Paths and Solvation Effects on the Molecular Mechanism for the Transposition of the α-Chlorocyclobutanone" @default.
- W2090759554 cites W1516933842 @default.
- W2090759554 cites W1963737263 @default.
- W2090759554 cites W1965028049 @default.
- W2090759554 cites W1965859561 @default.
- W2090759554 cites W1978958540 @default.
- W2090759554 cites W1980444846 @default.
- W2090759554 cites W1982164663 @default.
- W2090759554 cites W1984614201 @default.
- W2090759554 cites W1985305274 @default.
- W2090759554 cites W1990963853 @default.
- W2090759554 cites W1999970382 @default.
- W2090759554 cites W2002375571 @default.
- W2090759554 cites W2006806329 @default.
- W2090759554 cites W2009556603 @default.
- W2090759554 cites W2014936180 @default.
- W2090759554 cites W2016726234 @default.
- W2090759554 cites W2020895640 @default.
- W2090759554 cites W2022502585 @default.
- W2090759554 cites W2023271753 @default.
- W2090759554 cites W2025343510 @default.
- W2090759554 cites W2028973010 @default.
- W2090759554 cites W2031145826 @default.
- W2090759554 cites W2033387556 @default.
- W2090759554 cites W2035839127 @default.
- W2090759554 cites W2037117988 @default.
- W2090759554 cites W2038045242 @default.
- W2090759554 cites W2039161092 @default.
- W2090759554 cites W2042313414 @default.
- W2090759554 cites W2044940020 @default.
- W2090759554 cites W2044940178 @default.
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- W2090759554 cites W2056564220 @default.
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- W2090759554 cites W2059736106 @default.
- W2090759554 cites W2060149917 @default.
- W2090759554 cites W2067694497 @default.
- W2090759554 cites W2068511421 @default.
- W2090759554 cites W2069430316 @default.
- W2090759554 cites W2079301832 @default.
- W2090759554 cites W2079458939 @default.
- W2090759554 cites W2081159460 @default.
- W2090759554 cites W2083734450 @default.
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- W2090759554 cites W2086957099 @default.
- W2090759554 cites W2089759714 @default.
- W2090759554 cites W2095132836 @default.
- W2090759554 cites W2095229878 @default.
- W2090759554 cites W2100917738 @default.
- W2090759554 cites W2106957476 @default.
- W2090759554 cites W2132548730 @default.
- W2090759554 cites W2133524519 @default.
- W2090759554 cites W2143981217 @default.
- W2090759554 cites W2166016815 @default.
- W2090759554 cites W2317934327 @default.
- W2090759554 cites W2319761281 @default.
- W2090759554 cites W2323558989 @default.
- W2090759554 cites W2328340213 @default.
- W2090759554 cites W2328815296 @default.
- W2090759554 cites W2330440922 @default.
- W2090759554 cites W2330669340 @default.
- W2090759554 cites W2949096586 @default.
- W2090759554 cites W2949203728 @default.
- W2090759554 cites W2949251425 @default.
- W2090759554 cites W2950101506 @default.
- W2090759554 cites W2951358867 @default.
- W2090759554 cites W2951922604 @default.
- W2090759554 cites W2951989616 @default.
- W2090759554 cites W4247298585 @default.
- W2090759554 cites W4250731460 @default.
- W2090759554 cites W1966080525 @default.
- W2090759554 doi "https://doi.org/10.1021/ja962571q" @default.
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