Abstract
A dealkylation reaction of tertiary amines using chloroformate was a useful method for synthesizing morphinan derivatives without 17-substituents; however, the reaction has been applied to only the 14-hydromorphinans. In the course of the investigation of the 17-dealkylation reaction in 14-hydroxymorphinan, the novel cleavage reaction of the C16–N17 bond in the naltrexone derivative was found. A plausible reaction mechanism based on the stereoelectronic effect is presented. The examinations of dealkylation reactions in general tertiary amines ranked the tendency of cleavage as follows: benzyl>cyclopropylmethyl (CPM)≈allyl>methyl, ethyl. The preferable cleavage of the CPM group may be explained by the polarization of CPM–N17 bond due to a postulation of extreme stability of the cyclopropylcarbinyl cation.
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