Convergent and Biomimetic Enantioselective Total Synthesis of (−)-Communesin F
The first biomimetic enantioselective total synthesis of (-)-communesin F based on a late-stage heterodimerization and aminal exchange is described. Our synthesis features the expedient diazene-directed assembly of two advanced fragments to secure the congested C3a-C3a′ linkage in three steps, follo...
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| Format: | Article |
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American Chemical Society (ACS)
2018
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| Online Access: | http://hdl.handle.net/1721.1/114840 https://orcid.org/0000-0001-7761-085X https://orcid.org/0000-0001-5955-7653 https://orcid.org/0000-0003-3080-1063 |
| _version_ | 1811097293368066048 |
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| author | Lathrop, Stephen Pompeo, Matthew M Chang, Wen-Tau Movassaghi, Mohammad |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Lathrop, Stephen Pompeo, Matthew M Chang, Wen-Tau Movassaghi, Mohammad |
| author_sort | Lathrop, Stephen |
| collection | MIT |
| description | The first biomimetic enantioselective total synthesis of (-)-communesin F based on a late-stage heterodimerization and aminal exchange is described. Our synthesis features the expedient diazene-directed assembly of two advanced fragments to secure the congested C3a-C3a′ linkage in three steps, followed by a highly efficient biogenetically inspired aminal reorganization to access the heptacyclic communesin core in only two additional steps. Enantioselective syntheses of the two fragments were developed, with highlights including the catalytic asymmetric halocyclization and diastereoselective oxyamination reactions of tryptamine derivatives, a stereoselective sulfinimine allylation, and an efficient cyclotryptamine-C3a-sulfamate synthesis by either a new silver-promoted nucleophilic amination or a rhodium-catalyzed C-H amination protocol. The versatile syntheses of the fragments, their stereocontrolled assembly, and the efficient aminal exchange as supported by in situ monitoring experiments, in addition to the final stage N1′-acylation of the communesin core, provide a highly convergent synthesis of (-)-communesin F. |
| first_indexed | 2024-09-23T16:57:29Z |
| format | Article |
| id | mit-1721.1/114840 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T16:57:29Z |
| publishDate | 2018 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1148402022-10-03T09:24:57Z Convergent and Biomimetic Enantioselective Total Synthesis of (−)-Communesin F Lathrop, Stephen Pompeo, Matthew M Chang, Wen-Tau Movassaghi, Mohammad Massachusetts Institute of Technology. Department of Chemistry Lathrop, Stephen Pompeo, Matthew M Chang, Wen-Tau Movassaghi, Mohammad The first biomimetic enantioselective total synthesis of (-)-communesin F based on a late-stage heterodimerization and aminal exchange is described. Our synthesis features the expedient diazene-directed assembly of two advanced fragments to secure the congested C3a-C3a′ linkage in three steps, followed by a highly efficient biogenetically inspired aminal reorganization to access the heptacyclic communesin core in only two additional steps. Enantioselective syntheses of the two fragments were developed, with highlights including the catalytic asymmetric halocyclization and diastereoselective oxyamination reactions of tryptamine derivatives, a stereoselective sulfinimine allylation, and an efficient cyclotryptamine-C3a-sulfamate synthesis by either a new silver-promoted nucleophilic amination or a rhodium-catalyzed C-H amination protocol. The versatile syntheses of the fragments, their stereocontrolled assembly, and the efficient aminal exchange as supported by in situ monitoring experiments, in addition to the final stage N1′-acylation of the communesin core, provide a highly convergent synthesis of (-)-communesin F. National Institute of General Medical Sciences (U.S.) (GM089732) National Science Foundation (U.S.) (CHE1212527) Ruth L. Kirschstein National Research Service Award ((F32GM097776) Natural Sciences and Engineering Research Council of Canada (PGS D3 Scholarship) 2018-04-20T21:22:15Z 2018-04-20T21:22:15Z 2016-05 2016-04 2018-01-30T18:46:31Z Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/114840 Lathrop, Stephen P., Matthew Pompeo, Wen-Tau T. Chang, and Mohammad Movassaghi. “Convergent and Biomimetic Enantioselective Total Synthesis of (−)-Communesin F.” Journal of the American Chemical Society 138, no. 24 (June 14, 2016): 7763–7769. https://orcid.org/0000-0001-7761-085X https://orcid.org/0000-0001-5955-7653 https://orcid.org/0000-0003-3080-1063 http://dx.doi.org/10.1021/JACS.6B04072 Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) PMC |
| spellingShingle | Lathrop, Stephen Pompeo, Matthew M Chang, Wen-Tau Movassaghi, Mohammad Convergent and Biomimetic Enantioselective Total Synthesis of (−)-Communesin F |
| title | Convergent and Biomimetic Enantioselective Total Synthesis of (−)-Communesin F |
| title_full | Convergent and Biomimetic Enantioselective Total Synthesis of (−)-Communesin F |
| title_fullStr | Convergent and Biomimetic Enantioselective Total Synthesis of (−)-Communesin F |
| title_full_unstemmed | Convergent and Biomimetic Enantioselective Total Synthesis of (−)-Communesin F |
| title_short | Convergent and Biomimetic Enantioselective Total Synthesis of (−)-Communesin F |
| title_sort | convergent and biomimetic enantioselective total synthesis of communesin f |
| url | http://hdl.handle.net/1721.1/114840 https://orcid.org/0000-0001-7761-085X https://orcid.org/0000-0001-5955-7653 https://orcid.org/0000-0003-3080-1063 |
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