A reductive coupling strategy towards ripostatin A
Synthetic studies on the antibiotic natural product ripostatin A have been carried out with the aim to construct the C9−C10 bond by a nickel(0)-catalyzed coupling reaction of an enyne and an epoxide, followed by rearrangement of the resulting dienylcyclopropane intermediate to afford the skipped 1,4...
| Main Authors: | , |
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| Other Authors: | |
| Format: | Article |
| Language: | en_US |
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Beilstein-Institut
2013
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| Online Access: | http://hdl.handle.net/1721.1/82124 https://orcid.org/0000-0002-8601-7799 |
| _version_ | 1826190149104435200 |
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| author | Schleicher, Kristin D. Jamison, Timothy F. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Schleicher, Kristin D. Jamison, Timothy F. |
| author_sort | Schleicher, Kristin D. |
| collection | MIT |
| description | Synthetic studies on the antibiotic natural product ripostatin A have been carried out with the aim to construct the C9−C10 bond by a nickel(0)-catalyzed coupling reaction of an enyne and an epoxide, followed by rearrangement of the resulting dienylcyclopropane intermediate to afford the skipped 1,4,7-triene. A cyclopropyl enyne fragment corresponding to C1−C9 has been synthesized in high yield and demonstrated to be a competent substrate for the nickel(0)-catalyzed coupling with a model epoxide. Several synthetic approaches toward the C10−C26 epoxide have been pursued. The C13 stereocenter can be set by allylation and reductive decyanation of a cyanohydrin acetonide. A mild, fluoride-promoted decarboxylation enables construction of the C15−C16 bond by an aldol reaction. The product of this transformation is of the correct oxidation state and potentially three steps removed from the targeted epoxide fragment. |
| first_indexed | 2024-09-23T08:35:47Z |
| format | Article |
| id | mit-1721.1/82124 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T08:35:47Z |
| publishDate | 2013 |
| publisher | Beilstein-Institut |
| record_format | dspace |
| spelling | mit-1721.1/821242022-09-23T13:07:52Z A reductive coupling strategy towards ripostatin A Schleicher, Kristin D. Jamison, Timothy F. Massachusetts Institute of Technology. Department of Chemistry Schleicher, Kristin D. Jamison, Timothy F. Synthetic studies on the antibiotic natural product ripostatin A have been carried out with the aim to construct the C9−C10 bond by a nickel(0)-catalyzed coupling reaction of an enyne and an epoxide, followed by rearrangement of the resulting dienylcyclopropane intermediate to afford the skipped 1,4,7-triene. A cyclopropyl enyne fragment corresponding to C1−C9 has been synthesized in high yield and demonstrated to be a competent substrate for the nickel(0)-catalyzed coupling with a model epoxide. Several synthetic approaches toward the C10−C26 epoxide have been pursued. The C13 stereocenter can be set by allylation and reductive decyanation of a cyanohydrin acetonide. A mild, fluoride-promoted decarboxylation enables construction of the C15−C16 bond by an aldol reaction. The product of this transformation is of the correct oxidation state and potentially three steps removed from the targeted epoxide fragment. National Institute of General Medical Sciences (U.S.) Novartis (Firm) 2013-11-15T16:27:25Z 2013-11-15T16:27:25Z 2013-07 2013-05 Article http://purl.org/eprint/type/JournalArticle 1860-5397 http://hdl.handle.net/1721.1/82124 Schleicher, Kristin D, and Timothy F Jamison. “A reductive coupling strategy towards ripostatin A.” Beilstein Journal of Organic Chemistry 9 (July 31, 2013): 1533-1550. https://orcid.org/0000-0002-8601-7799 en_US http://dx.doi.org/10.3762/bjoc.9.175 Beilstein Journal of Organic Chemistry Creative Commons Attribution http://creativecommons.org/licenses/by/2.0 application/pdf Beilstein-Institut PMC |
| spellingShingle | Schleicher, Kristin D. Jamison, Timothy F. A reductive coupling strategy towards ripostatin A |
| title | A reductive coupling strategy towards ripostatin A |
| title_full | A reductive coupling strategy towards ripostatin A |
| title_fullStr | A reductive coupling strategy towards ripostatin A |
| title_full_unstemmed | A reductive coupling strategy towards ripostatin A |
| title_short | A reductive coupling strategy towards ripostatin A |
| title_sort | reductive coupling strategy towards ripostatin a |
| url | http://hdl.handle.net/1721.1/82124 https://orcid.org/0000-0002-8601-7799 |
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