Late transition metal catalyzed C-N and C-C bond forming reactions
Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1999.
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| Format: | Thesis |
| Language: | eng |
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Massachusetts Institute of Technology
2005
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| Online Access: | http://hdl.handle.net/1721.1/9521 |
| _version_ | 1826210612333510656 |
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| author | Wolfe, John P. (John Perry), 1970- |
| author2 | Stephen L. Buchwald. |
| author_facet | Stephen L. Buchwald. Wolfe, John P. (John Perry), 1970- |
| author_sort | Wolfe, John P. (John Perry), 1970- |
| collection | MIT |
| description | Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1999. |
| first_indexed | 2024-09-23T14:52:43Z |
| format | Thesis |
| id | mit-1721.1/9521 |
| institution | Massachusetts Institute of Technology |
| language | eng |
| last_indexed | 2024-09-23T14:52:43Z |
| publishDate | 2005 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/95212019-09-19T21:29:38Z Late transition metal catalyzed C-N and C-C bond forming reactions Wolfe, John P. (John Perry), 1970- Stephen L. Buchwald. Massachusetts Institute of Technology. Dept. of Chemistry. Massachusetts Institute of Technology. Department of Chemistry Chemistry. Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1999. Includes bibliographical references. New methods for the palladium-catalyzed amination of aryl halides are described. Key to these is the development of new catalysts and reaction conditions for these transformations. Initially, P(o-tol)3 ligated palladium catalysts were investigated but gave way to systems that used chelating phosphine ligands which substantially expanded the scope of the catalytic amination methodology. Palladium catalyst systems based on BINAP ((2,2'-diphenylphosphino)-1, 1 '-binaphthyl) allowed for the transformation of a much wider range of amines and aryl halide substrates, as well as aryl triflates. Of practical significance was that the use of cesium carbonate as a base at 100 °C substantially increased the functional group tolerance of the method. Palladium catalysts supported by novel, bulky, electron-rich phosphine ligands are exceptionally effective in the C-N, C-0, and C-C coupling procedures. For some substrate combinations, these palladium catalysts are effective for the room-temperature catalytic amination of aryl chlorides. These palladium catalysts are also highly effective for Suzuki coupling reactions of aryl bromides and chlorides at room temperature. Suzuki coupling reactions of aryl bromides and aryl chlorides are effective at very low catalyst loadings (0.000001-0.005 mol % Pd for ArBr, 0.02-0.05 mol % for ArCI) at 100 °C, and reactions of hindered aryl halides or boronic acids are effected at moderate catalyst loadings (1 mol % Pd). The high reactivity of these catalysts towards aryl chlorides challenges the conventional dogma that chloride substrates cannot be transformed under mild conditions with palladium catalysts, and significantly expands the pool of substrates available for cross-coupling chemistry. by John P. Wolfe. Ph.D. 2005-08-22T19:00:52Z 2005-08-22T19:00:52Z 1999 1999 Thesis http://hdl.handle.net/1721.1/9521 43847293 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 261 p. 19319406 bytes 19319160 bytes application/pdf application/pdf application/pdf Massachusetts Institute of Technology |
| spellingShingle | Chemistry. Wolfe, John P. (John Perry), 1970- Late transition metal catalyzed C-N and C-C bond forming reactions |
| title | Late transition metal catalyzed C-N and C-C bond forming reactions |
| title_full | Late transition metal catalyzed C-N and C-C bond forming reactions |
| title_fullStr | Late transition metal catalyzed C-N and C-C bond forming reactions |
| title_full_unstemmed | Late transition metal catalyzed C-N and C-C bond forming reactions |
| title_short | Late transition metal catalyzed C-N and C-C bond forming reactions |
| title_sort | late transition metal catalyzed c n and c c bond forming reactions |
| topic | Chemistry. |
| url | http://hdl.handle.net/1721.1/9521 |
| work_keys_str_mv | AT wolfejohnpjohnperry1970 latetransitionmetalcatalyzedcnandccbondformingreactions |