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A DFT proton affinity study of vinyl and allyl anions of cyclic vinyl ethers and cycloalkenes

โœ Scribed by Trevor D. Power; John F. Sebastian

Publisher
Elsevier Science
Year
1999
Tongue
French
Weight
208 KB
Volume
40
Category
Article
ISSN
0040-4039

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โœฆ Synopsis

Proton affinities of vinyl and allyl anions of cyclic vinyl ethers and cycloalkenes obtained at the B3PW91 level with Davidson's modification of basis set aug-cc-pVDZ are presented to further explore deprotonation reactions of cyclic vinyl ethers. The presence of an oxygen atom ยขx to a vinyl anion has a clear acidifying effect. Relative proton affinities for 2,3-dihydrofuran and 2,3-dihydrooxepin are consistent with experimental results; however this is not the case for 2,3-dihydro-4H-pyran and 2,3,4,5-tetrahydrooxepin. Although gas-phase proton affinities may help to explain deprotonation of cyclic vinyl ethers with some alkyllithium reagents in solution, it clearly cannot be the only contributor. Other factors to consider include solvation, aggregation, and relative transition state energies.

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