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Primary products resulting from C-H insertion of Ad: into the inner C-H bonds (3′ and 5′ of the glucose moieties) of α-cyclodextrin thus far have never been identified, although the contact with these protons is expected to be quite close. Embedded within the crystal of the 1@2(6-Cy) complex, such a product might be quite strained. Thus the primarily formed tertiary alcohol at C-3′ could be oxidized by a Cannizzaro-like reaction to a ketone with concomitant extrusion of the reduced hydrocarbon 2. Admittedly, this is a more speculative explanation for the high yield of adamantane (2) observed only in this particular case.
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46
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note
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Thermal decomposition of the 1@2(6-Cy) complex at 230°C or 300°C also yields 2 as the major volatile compound. In these pyrolytic reactions a considerable amount of material decomposed so that quantitative yields are of little significance. An absolute yield of 12% was determined for 2 with a total recovery of adamantanyl residues of only 25% (by analysis of the compounds also found in photolytic experiments).
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47
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Minute amounts of a third cyclodextrin derivative can be traced, but only in experiments at low temperature.
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