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Ab initio studies of the allylic hydroxylation: DFT calculation on the reaction of 2-methyl-2-butene with selenium dioxide

✍ Scribed by Choon Sup Ra; Gyoosoon Park

Publisher: Elsevier Science
Year: 2003
Tongue: French
Weight: 266 KB
Volume: 44
Category: Article
ISSN: 0040-4039
DOI: 10.1016/s0040-4039(02)02715-6

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✦ Synopsis

The mechanism of the allylic oxidation of 2-methyl-2-butene with selenium dioxide has been investigated by ab initio quantum mechanics. Transition states for two major steps (an ene reaction and a [2,3]-sigmatropic rearrangement) of this reaction have been optimized by the B3LYP/6-311+G(d,p) method. A comparison of the energies of the transition states shows that the anti-endo and syn-endo approaches are the efficient routes in the ene reaction and the methyl (C4) group is sited in a pseudo-equatorial environment in cyclic transition states during the [2,3]-rearrangement. Calculations also show the kind of the terminal alkyl (C4) substituents may control (E)-selectivity in the formation of the allylic alcohols.

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