Enantioselective Total Synthesis of (−)-Acylfulvene and (−)- Irofulven
We report our full account of the enantioselective total synthesis of (−)-acylfulvene (1) and (−)-irofulven (2), which features metathesis reactions for the rapid assembly of the molecular framework of these antitumor agents. We discuss (1) the application of an Evans Cu-catalyzed aldol addition rea...
| Main Authors: | , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | en_US |
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American Chemical Society
2012
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| Online Access: | http://hdl.handle.net/1721.1/73652 https://orcid.org/0000-0003-3080-1063 |
| _version_ | 1811096842431102976 |
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| author | Movassaghi, Mohammad Piersanti, Giovanni Piizzi, Grazia Siegel, Dustin Scott |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Movassaghi, Mohammad Piersanti, Giovanni Piizzi, Grazia Siegel, Dustin Scott |
| author_sort | Movassaghi, Mohammad |
| collection | MIT |
| description | We report our full account of the enantioselective total synthesis of (−)-acylfulvene (1) and (−)-irofulven (2), which features metathesis reactions for the rapid assembly of the molecular framework of these antitumor agents. We discuss (1) the application of an Evans Cu-catalyzed aldol addition reaction using a strained cyclopropyl ketenethioacetal, (2) an efficient enyne ring-closing metathesis cascade reaction in a challenging setting, (3) the reagent IPNBSH for a late-stage reductive allylic transposition reaction, and (4) the final RCM/dehydrogenation sequence for the formation of (−)-acylfulvene (1) and (−)-irofulven (2). |
| first_indexed | 2024-09-23T16:49:54Z |
| format | Article |
| id | mit-1721.1/73652 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T16:49:54Z |
| publishDate | 2012 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | mit-1721.1/736522022-09-29T21:48:55Z Enantioselective Total Synthesis of (−)-Acylfulvene and (−)- Irofulven Movassaghi, Mohammad Piersanti, Giovanni Piizzi, Grazia Siegel, Dustin Scott Massachusetts Institute of Technology. Department of Chemistry Movassaghi, Mohammad Movassaghi, Mohammad Piersanti, Giovanni Piizzi, Grazia Siegel, Dustin Scott We report our full account of the enantioselective total synthesis of (−)-acylfulvene (1) and (−)-irofulven (2), which features metathesis reactions for the rapid assembly of the molecular framework of these antitumor agents. We discuss (1) the application of an Evans Cu-catalyzed aldol addition reaction using a strained cyclopropyl ketenethioacetal, (2) an efficient enyne ring-closing metathesis cascade reaction in a challenging setting, (3) the reagent IPNBSH for a late-stage reductive allylic transposition reaction, and (4) the final RCM/dehydrogenation sequence for the formation of (−)-acylfulvene (1) and (−)-irofulven (2). Damon Runyon Cancer Research Foundation (grant no. DRS-39-04) National Institutes of Health (U.S.) and National Institute of General Medical Sciences (U.S.) (grant no. GM074825) Amgen, Inc. AstraZeneca (Firm) 2012-10-05T15:42:49Z 2012-10-05T15:42:49Z 2009-11 2009-09 Article http://purl.org/eprint/type/JournalArticle 0022-3263 1520-6904 http://hdl.handle.net/1721.1/73652 Siegel, Dustin S. et al. “Enantioselective Total Synthesis of (−)-Acylfulvene and (−)-Irofulven.” The Journal of Organic Chemistry 74.24 (2009): 9292–9304. https://orcid.org/0000-0003-3080-1063 en_US http://dx.doi.org/10.1021/jo901926z Journal of Organic Chemistry 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 PMC |
| spellingShingle | Movassaghi, Mohammad Piersanti, Giovanni Piizzi, Grazia Siegel, Dustin Scott Enantioselective Total Synthesis of (−)-Acylfulvene and (−)- Irofulven |
| title | Enantioselective Total Synthesis of (−)-Acylfulvene and (−)- Irofulven |
| title_full | Enantioselective Total Synthesis of (−)-Acylfulvene and (−)- Irofulven |
| title_fullStr | Enantioselective Total Synthesis of (−)-Acylfulvene and (−)- Irofulven |
| title_full_unstemmed | Enantioselective Total Synthesis of (−)-Acylfulvene and (−)- Irofulven |
| title_short | Enantioselective Total Synthesis of (−)-Acylfulvene and (−)- Irofulven |
| title_sort | enantioselective total synthesis of acylfulvene and irofulven |
| url | http://hdl.handle.net/1721.1/73652 https://orcid.org/0000-0003-3080-1063 |
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