Formal synthesis of (−)-morphine from d-glucal based on the cascade Claisen rearrangement |
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Authors: | Hiroki Tanimoto |
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Affiliation: | Department of Applied Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan |
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Abstract: | The formal synthesis of (−)-morphine is described. The C-ring in morphine was prepared in an optically pure form from d-glucal using Ferrier’s carbocyclization reaction, and the vicinal tertiary and quaternary stereocenters in the C-ring were stereoselectively generated in a one-step reaction based on the cascade sequential Claisen rearrangement of an allylic vicinal diol derivative. After the one-step formation of the dibenzofuran structure, the intramolecular Friedel-Crafts type reaction effectively constructed the ABCE-phenanthrofuran skeleton. Introduction of a tosylamide function, followed by reductive cyclization furnished (−)-dihydroisocodeine, the known synthetic intermediate for (−)-morphine. |
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Keywords: | Morphine Dihydroisocodeine Total synthesis Cascade Claisen rearrangement Friedel-Crafts type cyclization |
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