Palani, Namasivayam ; Chadha, Anju ; Balasubramanian, Kalpattu K. (1998) Mechanism of lithium perchlorate/diethyl ether-catalyzed rearrangement of α- and β-endo- and -exo-dicyclopentadienyl vinyl ethers: use of deuterium labeling and a chiral probe Journal of Organic Chemistry, 63 (16). pp. 5318-5323. ISSN 0022-3263
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Official URL: http://pubs.acs.org/doi/abs/10.1021/jo970715t
Related URL: http://dx.doi.org/10.1021/jo970715t
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 the mechanism is nonconcerted and the recombination of the ion pair occurs at the dissociated stage and not the intimate ion-pair stage. Proof of this came from deuterium-labeling studies and the use of an optically pure starting material. Furthermore, that the ionic intermediate formed must be 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 benzoate derivative of the aldehydes formed from the optically pure vinyl ether.
Item Type: | Article |
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Source: | Copyright of this article belongs to American Chemical Society. |
ID Code: | 3706 |
Deposited On: | 18 Oct 2010 09:59 |
Last Modified: | 13 May 2011 06:51 |
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