Enantioselective total synthesis of (-)-deoxoapodine
The first enantioselective total synthesis of (−)-deoxoapodine is described. Our synthesis of this hexacyclic aspidosperma alkaloid includes an efficient molybdenum-catalyzed enantioselective ring-closing metathesis reaction for the desymmetrization of an advanced intermediate that introduces the C5...
| Main Authors: | , , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | English |
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Wiley
2020
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| Online Access: | https://hdl.handle.net/1721.1/125957 |
| _version_ | 1826192599838359552 |
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| author | Kang, Taek White, Kolby L. Mann, Tyler J. Hoveyda, Amir H. Movassaghi, Mohammad |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Kang, Taek White, Kolby L. Mann, Tyler J. Hoveyda, Amir H. Movassaghi, Mohammad |
| author_sort | Kang, Taek |
| collection | MIT |
| description | The first enantioselective total synthesis of (−)-deoxoapodine is described. Our synthesis of this hexacyclic aspidosperma alkaloid includes an efficient molybdenum-catalyzed enantioselective ring-closing metathesis reaction for the desymmetrization of an advanced intermediate that introduces the C5-quaternary stereocenter. After C21-oxygenation, the pentacyclic core was accessed by electrophilic C19-amide activation and transannular spirocyclization. A biogenetically inspired dehydrative C6-etherification reaction proved highly effective to secure the F-ring and the fourth contiguous stereocenter of (−)-deoxoapodine with complete stereochemical control. |
| first_indexed | 2024-09-23T09:24:03Z |
| format | Article |
| id | mit-1721.1/125957 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T09:24:03Z |
| publishDate | 2020 |
| publisher | Wiley |
| record_format | dspace |
| spelling | mit-1721.1/1259572022-09-30T14:23:36Z Enantioselective total synthesis of (-)-deoxoapodine Kang, Taek White, Kolby L. Mann, Tyler J. Hoveyda, Amir H. Movassaghi, Mohammad Massachusetts Institute of Technology. Department of Chemistry The first enantioselective total synthesis of (−)-deoxoapodine is described. Our synthesis of this hexacyclic aspidosperma alkaloid includes an efficient molybdenum-catalyzed enantioselective ring-closing metathesis reaction for the desymmetrization of an advanced intermediate that introduces the C5-quaternary stereocenter. After C21-oxygenation, the pentacyclic core was accessed by electrophilic C19-amide activation and transannular spirocyclization. A biogenetically inspired dehydrative C6-etherification reaction proved highly effective to secure the F-ring and the fourth contiguous stereocenter of (−)-deoxoapodine with complete stereochemical control. NIH-NIGMS (grant no. GM074825) 2020-06-23T19:56:10Z 2020-06-23T19:56:10Z 2017-09-27 2017-08-07 2019-12-27T19:17:20Z Article http://purl.org/eprint/type/JournalArticle 1433-7851 https://hdl.handle.net/1721.1/125957 Kang, Taek, et al., "Enantioselective total synthesis of (-)-deoxoapodine." Angewandte Chemie International Edition 56, 44 (Sept. 2017): p. 13857-60 doi 10.1002/anie.201708088 ©2017 Author(s) en 10.1002/anie.201708088 Angewandte Chemie International Edition Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Wiley PMC |
| spellingShingle | Kang, Taek White, Kolby L. Mann, Tyler J. Hoveyda, Amir H. Movassaghi, Mohammad Enantioselective total synthesis of (-)-deoxoapodine |
| title | Enantioselective total synthesis of (-)-deoxoapodine |
| title_full | Enantioselective total synthesis of (-)-deoxoapodine |
| title_fullStr | Enantioselective total synthesis of (-)-deoxoapodine |
| title_full_unstemmed | Enantioselective total synthesis of (-)-deoxoapodine |
| title_short | Enantioselective total synthesis of (-)-deoxoapodine |
| title_sort | enantioselective total synthesis of deoxoapodine |
| url | https://hdl.handle.net/1721.1/125957 |
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