By R.C. Bingham, P.R.v. Schleyer

Content material: contemporary advancements within the chemistry of adamantane and comparable polycyclic hydrocarbons / via R.C. Bingham and P.V.R. Schleyer

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Under dilute reaction conditions, 3-homoadamantyl carboxylic acid is obtained as the only product. More concentrated reaction conditions allow intermolecular hydride shifts to occur. A product mixture consisting of both 3-homoadamantyl carboxylic acid and the corresponding 1-acid is obtained 137). In the analogous Ritter reaction (cf. Eq. (55)), intermolecular hydride shifts are not detected. In this case, the overall reaction seems to be thermodynamically controlled, with the major product at long reaction times being the unrearranged 1-adamantylcarbinyl acetamide 137a).

The/3-equatorial substituted haloadamantanones, on the other hand, exhibit extraordinarily high circular dichroism absorptions. High order anisotropy terms explain these observations 186). The rigidity of the adamantanone system has also been used to demonstrate that c~-equatorial substituents make only very small small rotatory contributions 186a). 51 V. Chemical Properties A. Substitution Methods 1. Ionic Reactions Although the bridgehead positions of many polycyclic hydrocarbons have been found to be quite unreactive toward nucleophilic substitutions 1s7), the 1-adamantyl cation may be generated with relative ease.

Cf Ref. 155)). l-adamantyl cation appear furthest downfield. This "anomalous" chemical shift is also observed in the spectrum of the i-diamantyl cation (58) obtained from the SbFs-FSO3H solution of diamantane 157). 67 ppm 58 This 7-deshielding effect might be explained on the basis of a special cage effect which enables the back lobes of the bridgehead C-H bonds to overlap with the vacant p-orbital of the cation 156). No direct experimental evidence exists which would substantiate this special cage effect, however.

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