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Application of α-alkoxy bridgehead radical for coupling of oxygenated carbocycles
Daisuke Urabe1, Hiroki Yamaguchi, Masayuki Inoue
1Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Tokyo 113-0033, Japan.
Abstract:
A new coupling methodology for assembly of highly oxygenated carbocycles was developed. An α-alkoxy bridgehead radical was employed as the key reactive intermediate due to its potent reactivity, minimum steric interaction, and predestined stereochemical outcome. The radical of the trioxadamantane structure, generated from the O,Se-acetal, was reacted with electron-deficient cyclic olefins of various ring sizes. Intermolecular formation of sterically congested linkages between two tetrasubstituted carbons and application of the method to a three-component coupling were two significant achievements.
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