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Hyperconjugative Effects in the Stereoselective Ring-Opening Reactions of Oxetenoxides

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journal contribution
posted on 28.10.2004, 00:00 by Seiji Mori, Mitsuru Shindo
Unexpectedly, the pattern of the stereoselectivity in the ring-opening reactions of lithium oxetenoxides is not consistent with the bulkiness of substituents, and both the bulkier tert-butyl and silyl substituents favor inward rotation. With the aid of B3LYP calculations, the hyperconjugative interaction between the breaking C1−O σ and its anti-periplanar Z-Me (Z = Si or C) σ* orbital is found to be responsible among the secondary orbital interactions of the substituents and the oxetene moiety.

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