Catalyst-Controlled Stereoselective Olefin Metathesis as a Principal Strategy in Multistep Synthesis Design: A Concise Route to (+)-Neopeltolide
Molybdenum-, tungsten-, and ruthenium-based complexes that control the stereochemical outcome of olefin metathesis reactions have been recently introduced. However, the complementary nature of these systems through their combined use in multistep complex molecule synthesis has not been illustrated....
| Main Authors: | , , |
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| Format: | Article |
| Language: | en_US |
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John Wiley & Sons
2016
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| Online Access: | http://hdl.handle.net/1721.1/103915 https://orcid.org/0000-0001-5827-3552 |
| _version_ | 1826211372661211136 |
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| author | Yu, Miao Schrock, Richard Royce Hoveyda, Amir H. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Yu, Miao Schrock, Richard Royce Hoveyda, Amir H. |
| author_sort | Yu, Miao |
| collection | MIT |
| description | Molybdenum-, tungsten-, and ruthenium-based complexes that control the stereochemical outcome of olefin metathesis reactions have been recently introduced. However, the complementary nature of these systems through their combined use in multistep complex molecule synthesis has not been illustrated. A concise diastereo- and enantioselective route that furnishes the anti-proliferative natural product neopeltolide is now disclosed. Catalytic transformations are employed to address every stereochemical issue. Among the featured processes are an enantioselective ring-opening/cross-metathesis promoted by a Mo monoaryloxide pyrrolide (MAP) complex and a macrocyclic ring-closing metathesis that affords a trisubstituted alkene and is catalyzed by a Mo bis(aryloxide) species. Furthermore, Z-selective cross-metathesis reactions, facilitated by Mo and Ru complexes, have been employed in the stereoselective synthesis of the acyclic dienyl moiety of the target molecule. |
| first_indexed | 2024-09-23T15:05:11Z |
| format | Article |
| id | mit-1721.1/103915 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T15:05:11Z |
| publishDate | 2016 |
| publisher | John Wiley & Sons |
| record_format | dspace |
| spelling | mit-1721.1/1039152022-10-02T00:29:33Z Catalyst-Controlled Stereoselective Olefin Metathesis as a Principal Strategy in Multistep Synthesis Design: A Concise Route to (+)-Neopeltolide Yu, Miao Schrock, Richard Royce Hoveyda, Amir H. Massachusetts Institute of Technology. Department of Chemistry Schrock, Richard Royce Molybdenum-, tungsten-, and ruthenium-based complexes that control the stereochemical outcome of olefin metathesis reactions have been recently introduced. However, the complementary nature of these systems through their combined use in multistep complex molecule synthesis has not been illustrated. A concise diastereo- and enantioselective route that furnishes the anti-proliferative natural product neopeltolide is now disclosed. Catalytic transformations are employed to address every stereochemical issue. Among the featured processes are an enantioselective ring-opening/cross-metathesis promoted by a Mo monoaryloxide pyrrolide (MAP) complex and a macrocyclic ring-closing metathesis that affords a trisubstituted alkene and is catalyzed by a Mo bis(aryloxide) species. Furthermore, Z-selective cross-metathesis reactions, facilitated by Mo and Ru complexes, have been employed in the stereoselective synthesis of the acyclic dienyl moiety of the target molecule. National Institutes of Health (U.S.) (NIH grant GM-59426) National Institutes of Health (U.S.) (NIH grant GM-57212) AstraZeneca (Firm) (Graduate Fellowship) National Science Foundation (U.S.) (NSF award CHE-1362763) 2016-08-15T18:29:19Z 2016-08-15T18:29:19Z 2014-11 Article http://purl.org/eprint/type/JournalArticle 14337851 http://hdl.handle.net/1721.1/103915 Yu, Miao, Richard R. Schrock, and Amir H. Hoveyda. "Catalyst-Controlled Stereoselective Olefin Metathesis as a Principal Strategy in Multistep Synthesis Design: A Concise Route to (+)-Neopeltolide." Angewandte Chemie International Edition 54:1 (2014), pp.215-220. https://orcid.org/0000-0001-5827-3552 en_US http://dx.doi.org/10.1002/anie.201409120 Angewandte Chemie International Edition Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf John Wiley & Sons PMC |
| spellingShingle | Yu, Miao Schrock, Richard Royce Hoveyda, Amir H. Catalyst-Controlled Stereoselective Olefin Metathesis as a Principal Strategy in Multistep Synthesis Design: A Concise Route to (+)-Neopeltolide |
| title | Catalyst-Controlled Stereoselective Olefin Metathesis as a Principal Strategy in Multistep Synthesis Design: A Concise Route to (+)-Neopeltolide |
| title_full | Catalyst-Controlled Stereoselective Olefin Metathesis as a Principal Strategy in Multistep Synthesis Design: A Concise Route to (+)-Neopeltolide |
| title_fullStr | Catalyst-Controlled Stereoselective Olefin Metathesis as a Principal Strategy in Multistep Synthesis Design: A Concise Route to (+)-Neopeltolide |
| title_full_unstemmed | Catalyst-Controlled Stereoselective Olefin Metathesis as a Principal Strategy in Multistep Synthesis Design: A Concise Route to (+)-Neopeltolide |
| title_short | Catalyst-Controlled Stereoselective Olefin Metathesis as a Principal Strategy in Multistep Synthesis Design: A Concise Route to (+)-Neopeltolide |
| title_sort | catalyst controlled stereoselective olefin metathesis as a principal strategy in multistep synthesis design a concise route to neopeltolide |
| url | http://hdl.handle.net/1721.1/103915 https://orcid.org/0000-0001-5827-3552 |
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