Concise and Enantioselective Total Synthesis of (−)-Mehranine, (−)-Methylenebismehranine, and Related
We report an efficient and highly stereoselective strategy for the synthesis of Aspidosperma alkaloids based on the transannular cyclization of a chiral lactam precursor. Three new stereocenters are formed in this key step with excellent diastereoselectivity due to the conformational bias of the cyc...
| Main Authors: | , , |
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| Other Authors: | |
| Format: | Article |
| Language: | en_US |
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Wiley Blackwell
2017
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| Online Access: | http://hdl.handle.net/1721.1/110416 https://orcid.org/0000-0003-3080-1063 |
| _version_ | 1826202511786115072 |
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| author | Mewald, Marius Medley, Jonathan William Movassaghi, Mohammad |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Mewald, Marius Medley, Jonathan William Movassaghi, Mohammad |
| author_sort | Mewald, Marius |
| collection | MIT |
| description | We report an efficient and highly stereoselective strategy for the synthesis of Aspidosperma alkaloids based on the transannular cyclization of a chiral lactam precursor. Three new stereocenters are formed in this key step with excellent diastereoselectivity due to the conformational bias of the cyclization precursor, leading to a versatile pentacyclic intermediate. A subsequent stereoselective epoxidation followed by a mild formamide reduction enabled the first total synthesis of the Aspidosperma alkaloids (−)-mehranine and (+)-(6S,7S)-dihydroxy-N-methylaspidospermidine. A late-stage dimerization of (−)-mehranine mediated by scandium trifluoromethanesulfonate completed the first total synthesis of (−)-methylenebismehranine. |
| first_indexed | 2024-09-23T12:08:40Z |
| format | Article |
| id | mit-1721.1/110416 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T12:08:40Z |
| publishDate | 2017 |
| publisher | Wiley Blackwell |
| record_format | dspace |
| spelling | mit-1721.1/1104162022-09-28T00:28:39Z Concise and Enantioselective Total Synthesis of (−)-Mehranine, (−)-Methylenebismehranine, and Related Mewald, Marius Medley, Jonathan William Movassaghi, Mohammad Massachusetts Institute of Technology. Department of Chemistry Mewald, Marius Medley, Jonathan William Movassaghi, Mohammad We report an efficient and highly stereoselective strategy for the synthesis of Aspidosperma alkaloids based on the transannular cyclization of a chiral lactam precursor. Three new stereocenters are formed in this key step with excellent diastereoselectivity due to the conformational bias of the cyclization precursor, leading to a versatile pentacyclic intermediate. A subsequent stereoselective epoxidation followed by a mild formamide reduction enabled the first total synthesis of the Aspidosperma alkaloids (−)-mehranine and (+)-(6S,7S)-dihydroxy-N-methylaspidospermidine. A late-stage dimerization of (−)-mehranine mediated by scandium trifluoromethanesulfonate completed the first total synthesis of (−)-methylenebismehranine. National Institute of General Medical Sciences (U.S.) (GM074825) 2017-07-03T13:30:56Z 2017-07-03T13:30:56Z 2014-10 2014-05 Article http://purl.org/eprint/type/JournalArticle 1433-7851 1521-3773 http://hdl.handle.net/1721.1/110416 Mewald, Marius; Medley, Jonathan William and Movassaghi, Mohammad. “ Concise and Enantioselective Total Synthesis of (−)-Mehranine, (−)-Methylenebismehranine, and Related Aspidosperma Alkaloids .”Angewandte Chemie International Edition 53, 43 (September 2014): 11634–11639 © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim https://orcid.org/0000-0003-3080-1063 en_US http://dx.doi.org/10.1002/anie.201405609 Angewandte Chemie International Edition Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Wiley Blackwell PMC |
| spellingShingle | Mewald, Marius Medley, Jonathan William Movassaghi, Mohammad Concise and Enantioselective Total Synthesis of (−)-Mehranine, (−)-Methylenebismehranine, and Related |
| title | Concise and Enantioselective Total Synthesis of (−)-Mehranine, (−)-Methylenebismehranine, and Related |
| title_full | Concise and Enantioselective Total Synthesis of (−)-Mehranine, (−)-Methylenebismehranine, and Related |
| title_fullStr | Concise and Enantioselective Total Synthesis of (−)-Mehranine, (−)-Methylenebismehranine, and Related |
| title_full_unstemmed | Concise and Enantioselective Total Synthesis of (−)-Mehranine, (−)-Methylenebismehranine, and Related |
| title_short | Concise and Enantioselective Total Synthesis of (−)-Mehranine, (−)-Methylenebismehranine, and Related |
| title_sort | concise and enantioselective total synthesis of mehranine methylenebismehranine and related |
| url | http://hdl.handle.net/1721.1/110416 https://orcid.org/0000-0003-3080-1063 |
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