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American Chemical Society

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The Journal of Organic Chemistry

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Access to each CC face of adamantylideneadamantane (AA) and sesquihomoadamantene (SA) is hindered by the hydrogenic canopy consisting of four β-hydrogens; otherwise, these olefins have quite normal environments. X-ray crystallography and density functional (DFT) calculations show a 0.5 Å larger annular opening in the protective cover of AA than that in SA. This contributes to the remarkable differences in reactivity toward various reagents, not only by limiting access to the olefin site in SA but also by inhibiting reactions which force these hydrogens closer together. Thus, AA is subject to typical olefin-addition reactions with bromine, sulfuryl chloride, m-chloroperbenzoic acid, dioxygen, and so forth, albeit sometimes at attenuated rates. On the other hand, SA is singularly unreactive under identical reaction conditions, except for the notable exceptions that include Brønsted (protonic) acids, a nitrosonium cation, and dichlorine. The exceptions are characterized as three sterically limited (electrophilic) reagents whose unique reactivity patterns are shown to be strongly influenced by steric access to the CC center. As such, the different degrees of steric encumbrance in the isomeric donors AA and SA shed considerable light on the diverse nature of olefinic reactions. In particular, they evoke mechanistic features in electrophilic addition versus electron transfer, which are otherwise not readily discernible with other less hindered olefinic donors. Transient structures of the olefinic-reaction intermediates such as the protonated carbocations AA−H+ and SA−H+ as well as the cation radicals AA+ and SA+ are probed by the combination of X-ray crystallographic analyses and density functional theoretical computations.


Accepted version. The Journal of Organic Chemistry, Vol. 67, No. 15 (2002): 5106-5116. DOI. © 2002 American Chemical Society. Used with permission.

Sergey V. Lindeman and Rajendra Rathore were affiliated with the University of Houston at the time of publication.

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