| Abstract
| - Lithium perchlorate/diethyl ether (LPDE) mediated rearrangement of α- and β-endo-dicyclopentadienyl vinyl ethers 5 and 6 resulted in the formation of the aldehyde 8, indicating that themechanism is nonconcerted and the recombination of the ion pair occurs at the dissociated stageand not the intimate ion-pair stage. Proof of this came from deuterium-labeling studies and theuse of an optically pure starting material. Furthermore, that the ionic intermediate formed mustbe symmetrical resulting in enantiomeric aldehydes from both normal and allylic attack corresponding to products of formal 1,3 and 3,3 shifts was seen in the chiral analysis of the benzoatederivative of the aldehydes formed from the optically pure vinyl ether.
|
