A Dioxane Template for Highly Selective Epoxy Alcohol Cyclizations
Ladder polyether natural products are a class of natural products denoted by their high functional-group density and large number of well-defined stereocenters. They comprise the toxic component of harmful algal blooms (HABs), having significant negative economic and environmental ramifications. How...
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| Format: | Article |
| Language: | en_US |
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Wiley Blackwell
2015
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| Online Access: | http://hdl.handle.net/1721.1/94647 https://orcid.org/0000-0002-5712-9222 https://orcid.org/0000-0002-8601-7799 |
| _version_ | 1811087417619251200 |
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| author | Mousseau, James Morten, Christopher J. Jamison, Timothy F. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Mousseau, James Morten, Christopher J. Jamison, Timothy F. |
| author_sort | Mousseau, James |
| collection | MIT |
| description | Ladder polyether natural products are a class of natural products denoted by their high functional-group density and large number of well-defined stereocenters. They comprise the toxic component of harmful algal blooms (HABs), having significant negative economic and environmental ramifications. However, their mode of action, namely blocking various cellular ion channels, also denotes their promise as potential anticancer agents. Understanding their potential mode of biosynthesis will not only help with developing ways to limit the damage of HABs, but would also facilitate the synthesis of a range of analogs with interesting biological activity. 1,3-Dioxan-5-ol substrates display remarkable ‘enhanced template effects’ in water-promoted epoxide cyclization processes en route to the synthesis of these ladder polyether natural products. In many cases, they provide near complete endo-to-exo selectivity in the cyclization of epoxy alcohols, thereby strongly favoring the formation of tetrahydropyran (THP) over tetrahydrofuran (THF) rings. The effects of various Brønsted and Lewis acidic and basic conditions are explored to demonstrate the superior selectivity of the template over the previously reported THP-based epoxy alcohols. In addition, the consideration of other synthetic routes are also considered with the goal of gaining rapid access to a plethora of potential starting materials applicable towards the synthesis of ladder polyethers. Finally, cascade sequences with polyepoxides are investigated, further demonstrating the versatility of this new reaction template. |
| first_indexed | 2024-09-23T13:45:46Z |
| format | Article |
| id | mit-1721.1/94647 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:45:46Z |
| publishDate | 2015 |
| publisher | Wiley Blackwell |
| record_format | dspace |
| spelling | mit-1721.1/946472022-10-01T16:58:00Z A Dioxane Template for Highly Selective Epoxy Alcohol Cyclizations Mousseau, James Morten, Christopher J. Jamison, Timothy F. Massachusetts Institute of Technology. Department of Chemistry Jamison, Timothy F. Mousseau, James Morten, Christopher J. Ladder polyether natural products are a class of natural products denoted by their high functional-group density and large number of well-defined stereocenters. They comprise the toxic component of harmful algal blooms (HABs), having significant negative economic and environmental ramifications. However, their mode of action, namely blocking various cellular ion channels, also denotes their promise as potential anticancer agents. Understanding their potential mode of biosynthesis will not only help with developing ways to limit the damage of HABs, but would also facilitate the synthesis of a range of analogs with interesting biological activity. 1,3-Dioxan-5-ol substrates display remarkable ‘enhanced template effects’ in water-promoted epoxide cyclization processes en route to the synthesis of these ladder polyether natural products. In many cases, they provide near complete endo-to-exo selectivity in the cyclization of epoxy alcohols, thereby strongly favoring the formation of tetrahydropyran (THP) over tetrahydrofuran (THF) rings. The effects of various Brønsted and Lewis acidic and basic conditions are explored to demonstrate the superior selectivity of the template over the previously reported THP-based epoxy alcohols. In addition, the consideration of other synthetic routes are also considered with the goal of gaining rapid access to a plethora of potential starting materials applicable towards the synthesis of ladder polyethers. Finally, cascade sequences with polyepoxides are investigated, further demonstrating the versatility of this new reaction template. National Institute of General Medical Sciences (U.S.) (Grant GM72566) Natural Sciences and Engineering Research Council of Canada Fonds québécois de la recherche sur la nature et les technologies 2015-02-19T18:39:49Z 2015-02-19T18:39:49Z 2013-06 2013-03 Article http://purl.org/eprint/type/JournalArticle 09476539 1521-3765 http://hdl.handle.net/1721.1/94647 Mousseau, James J., Christopher J. Morten, and Timothy F. Jamison. “A Dioxane Template for Highly Selective Epoxy Alcohol Cyclizations.” Chem. Eur. J. 19, no. 30 (June 17, 2013): 10004–10016. https://orcid.org/0000-0002-5712-9222 https://orcid.org/0000-0002-8601-7799 en_US http://dx.doi.org/10.1002/chem.201300845 Chemistry - A European Journal Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Wiley Blackwell PMC |
| spellingShingle | Mousseau, James Morten, Christopher J. Jamison, Timothy F. A Dioxane Template for Highly Selective Epoxy Alcohol Cyclizations |
| title | A Dioxane Template for Highly Selective Epoxy Alcohol Cyclizations |
| title_full | A Dioxane Template for Highly Selective Epoxy Alcohol Cyclizations |
| title_fullStr | A Dioxane Template for Highly Selective Epoxy Alcohol Cyclizations |
| title_full_unstemmed | A Dioxane Template for Highly Selective Epoxy Alcohol Cyclizations |
| title_short | A Dioxane Template for Highly Selective Epoxy Alcohol Cyclizations |
| title_sort | dioxane template for highly selective epoxy alcohol cyclizations |
| url | http://hdl.handle.net/1721.1/94647 https://orcid.org/0000-0002-5712-9222 https://orcid.org/0000-0002-8601-7799 |
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