Mechanistic and synthetic studies of the intramolecular [4+2] cycloaddition of conjugated enynes
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2004.
| Main Author: | |
|---|---|
| Other Authors: | |
| Format: | Thesis |
| Language: | eng |
| Published: |
Massachusetts Institute of Technology
2005
|
| Subjects: | |
| Online Access: | http://hdl.handle.net/1721.1/17739 |
| _version_ | 1826213887285919744 |
|---|---|
| author | Hayes, Martin Elliott, 1974- |
| author2 | Rick L. Danheiser. |
| author_facet | Rick L. Danheiser. Hayes, Martin Elliott, 1974- |
| author_sort | Hayes, Martin Elliott, 1974- |
| collection | MIT |
| description | Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2004. |
| first_indexed | 2024-09-23T15:56:25Z |
| format | Thesis |
| id | mit-1721.1/17739 |
| institution | Massachusetts Institute of Technology |
| language | eng |
| last_indexed | 2024-09-23T15:56:25Z |
| publishDate | 2005 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/177392019-04-11T06:26:23Z Mechanistic and synthetic studies of the intramolecular [4+2] cycloaddition of conjugated enynes Hayes, Martin Elliott, 1974- Rick L. Danheiser. Massachusetts Institute of Technology. Dept. of Chemistry. Massachusetts Institute of Technology. Dept. of Chemistry. Chemistry. Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2004. Vita. Includes bibliographical references. An examination of the mechanism and scope of the intramolecular [4+2] cycloaddition of conjugated enynes has shown the reaction likely proceeds by a concerted cycloaddition of the enyne to give a highly reactive cyclic allene intermediate which isomerizes to aromatic and dihydroaromatic compounds through proton transfer or hydrogen atom transfer mechanisms. Studies of the intramolecular cycloaddition of conjugated arylacetylenes (arenynes) indicated that these compounds may react by a stepwise annulation mechanism involving biradical intermediates. An investigation of the use of protic solvents has shown that alcohols, in particular 2,2,2-trifluoroethanol, can significantly improve the isolated yield of products. The application of strained cyclic acetylenes, specifically arynes generated by a modification of the Kobayashi protocol with tetrabutylammonium triphenyldifluorosilicate (TBAT), has been shown to efficiently provide cycloaddition products with substituted enynes, arenynes, and hetarenynes at room temperature. by Martin Elliott Hayes. Ph.D. 2005-06-02T18:27:36Z 2005-06-02T18:27:36Z 2004 2004 Thesis http://hdl.handle.net/1721.1/17739 56481121 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 295 p. 7793498 bytes 7793300 bytes application/pdf application/pdf application/pdf Massachusetts Institute of Technology |
| spellingShingle | Chemistry. Hayes, Martin Elliott, 1974- Mechanistic and synthetic studies of the intramolecular [4+2] cycloaddition of conjugated enynes |
| title | Mechanistic and synthetic studies of the intramolecular [4+2] cycloaddition of conjugated enynes |
| title_full | Mechanistic and synthetic studies of the intramolecular [4+2] cycloaddition of conjugated enynes |
| title_fullStr | Mechanistic and synthetic studies of the intramolecular [4+2] cycloaddition of conjugated enynes |
| title_full_unstemmed | Mechanistic and synthetic studies of the intramolecular [4+2] cycloaddition of conjugated enynes |
| title_short | Mechanistic and synthetic studies of the intramolecular [4+2] cycloaddition of conjugated enynes |
| title_sort | mechanistic and synthetic studies of the intramolecular 4 2 cycloaddition of conjugated enynes |
| topic | Chemistry. |
| url | http://hdl.handle.net/1721.1/17739 |
| work_keys_str_mv | AT hayesmartinelliott1974 mechanisticandsyntheticstudiesoftheintramolecular42cycloadditionofconjugatedenynes |