Carbon-trifluoromethyl bond forming reactions and palladium-catalyzed cyanation of (hetero)aryl halides
Thesis (Ph. D. in Organic Chemistry)--Massachusetts Institute of Technology, Dept. of Chemistry, 2013.
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| Format: | Thesis |
| Language: | eng |
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Massachusetts Institute of Technology
2013
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| Online Access: | http://hdl.handle.net/1721.1/82321 |
| _version_ | 1811075846366035968 |
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| author | Senecal, Todd D. (Todd Dale) |
| author2 | Stephen L. Buchwald. |
| author_facet | Stephen L. Buchwald. Senecal, Todd D. (Todd Dale) |
| author_sort | Senecal, Todd D. (Todd Dale) |
| collection | MIT |
| description | Thesis (Ph. D. in Organic Chemistry)--Massachusetts Institute of Technology, Dept. of Chemistry, 2013. |
| first_indexed | 2024-09-23T10:12:40Z |
| format | Thesis |
| id | mit-1721.1/82321 |
| institution | Massachusetts Institute of Technology |
| language | eng |
| last_indexed | 2024-09-23T10:12:40Z |
| publishDate | 2013 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/823212019-04-10T23:57:34Z Carbon-trifluoromethyl bond forming reactions and palladium-catalyzed cyanation of (hetero)aryl halides Senecal, Todd D. (Todd Dale) Stephen L. Buchwald. Massachusetts Institute of Technology. Department of Chemistry. Massachusetts Institute of Technology. Department of Chemistry. Chemistry. Thesis (Ph. D. in Organic Chemistry)--Massachusetts Institute of Technology, Dept. of Chemistry, 2013. Cataloged from PDF version of thesis. Includes bibliographical references. Chapter 1 Nucleophilic trifluoromethyl sources were systematically examined in stoichiometric palladium experiments to determine the most efficient class of reagents for transmetallation. In conjunction with reductive elimination studies, this led to the development of the first system for the trifluoromethylation of aryl chlorides. Chapter 2 A method for the oxidative trifluoromethylation of (hetero)aryl boronic acids is reported. Bench top setup and visual reaction monitoring makes this process particularly well suited to medicinal and academic chemists. Fast reaction times allow for the trifluoromethylation of heterocyclic boronic acids that are prone to facile protodeboronation. Chapter 3 A trifluoromethylation of potassium vinyl trifluoroborates via iron catalysis has been developed. Excellent E:Z ratios are observed for styryl trifluoroborates. Initial investigations suggest a mechanistic pathway that diverges from our previous (hetero)aryl trifluoromethylation systems. Chapter 4 A highly efficient system for the palladium-catalyzed cyanation of (hetero)aryl halides is disclosed. By employing palladacycle precatalysts, cyanide binding during catalyst formation is minimized, allowing for low catalyst loadings even with unactivated aryl chlorides. The method utilizes a non-toxic cyanide source and exhibits excellent functional group tolerance, particularly of free N-H groups and typically challenging five membered heterocycles. by Todd D. Senecal. Ph.D.in Organic Chemistry 2013-11-18T19:08:36Z 2013-11-18T19:08:36Z 2013 2013 Thesis http://hdl.handle.net/1721.1/82321 861616137 eng M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. http://dspace.mit.edu/handle/1721.1/7582 377 p. application/pdf Massachusetts Institute of Technology |
| spellingShingle | Chemistry. Senecal, Todd D. (Todd Dale) Carbon-trifluoromethyl bond forming reactions and palladium-catalyzed cyanation of (hetero)aryl halides |
| title | Carbon-trifluoromethyl bond forming reactions and palladium-catalyzed cyanation of (hetero)aryl halides |
| title_full | Carbon-trifluoromethyl bond forming reactions and palladium-catalyzed cyanation of (hetero)aryl halides |
| title_fullStr | Carbon-trifluoromethyl bond forming reactions and palladium-catalyzed cyanation of (hetero)aryl halides |
| title_full_unstemmed | Carbon-trifluoromethyl bond forming reactions and palladium-catalyzed cyanation of (hetero)aryl halides |
| title_short | Carbon-trifluoromethyl bond forming reactions and palladium-catalyzed cyanation of (hetero)aryl halides |
| title_sort | carbon trifluoromethyl bond forming reactions and palladium catalyzed cyanation of hetero aryl halides |
| topic | Chemistry. |
| url | http://hdl.handle.net/1721.1/82321 |
| work_keys_str_mv | AT senecaltodddtodddale carbontrifluoromethylbondformingreactionsandpalladiumcatalyzedcyanationofheteroarylhalides |