Synthesis and applications of atropisomeric quinazolinone phosphine ligands
Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1998.
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| Format: | Thesis |
| Language: | eng |
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Massachusetts Institute of Technology
2009
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| Online Access: | http://hdl.handle.net/1721.1/47887 |
| _version_ | 1826216090820149248 |
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| author | Dai, Xuedong, 1970- |
| author2 | Scott C. Virgil. |
| author_facet | Scott C. Virgil. Dai, Xuedong, 1970- |
| author_sort | Dai, Xuedong, 1970- |
| collection | MIT |
| description | Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1998. |
| first_indexed | 2024-09-23T16:41:50Z |
| format | Thesis |
| id | mit-1721.1/47887 |
| institution | Massachusetts Institute of Technology |
| language | eng |
| last_indexed | 2024-09-23T16:41:50Z |
| publishDate | 2009 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/478872020-02-10T22:23:13Z Synthesis and applications of atropisomeric quinazolinone phosphine ligands Dai, Xuedong, 1970- Scott C. Virgil. Massachusetts Institute of Technology. Department of Chemistry Chemistry Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1998. Includes bibliographical references. Several novel atropisomeric phosphine ligands have been synthesized and evaluated. The syntheses of 2-methyl-3-[2'-(diphenylphosphino)phenyl]-4(3H)- quinazolinone (la) and its methyl-substituted analogs lb and ic were achieved in good yield by coupling N-acetylanthranilic acid with the corresponding phosphinoanilines 4a-c. A practical resolution of ligands la-c was accomplished using the benzenesulfonylhydrazone derivative (10) of (1S)-(+)-camphorsulfonic acid as a novel resolving agent. Several catalytic reactions including palladium-catalyzed asymmetric allylic alkylation, phosphine-catalyzed [3+2] cycloaddition of N-tosylimines with 2,3- butadienoate, and asymmetric intramolecular Heck reaction were performed. The 2-methyl group of this ligand series could be activated into the olefin form in the presence of Rh(nbd)2C104. The rhodium complex was found to be able to catalyze conjugate addition of the Grignard reagent (n-BuMgBr) to enones. The synthesis of 3-[4',6'-dimethyl-2'-(diphenylphosphino)phenyl]-4(3H)- quinazolinone (id) was achieved by coupling 4H-3,1-benzoxazin-4-one (71) with 4,6- dimethyl-2-diphenylphosphinoaniline (4c). Ligand ld could be directly lithiated by lithium diisopropylamide (LDA). The hetero-substituted analogs le-g were synthesized in good yield by quenching the lithium anion of ligand id with electrophiles. Resolutions of ligands id and le were achieved using (-)-di-p-chloro-bis[(S)-dimethyl-(1- naphthylethyl)aminato-C 2 , N]dipalladium(II) (78) and (-)-di-ji-chloro-bis[(S)-dimethyl-(1- phenylethyl)aminato-C 2 , N]dipalladium(II) (7), respectively. by Xuedong Dai. Ph.D. 2009-10-01T15:58:48Z 2009-10-01T15:58:48Z 1998 1998 Thesis http://hdl.handle.net/1721.1/47887 43379539 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 187 leaves application/pdf Massachusetts Institute of Technology |
| spellingShingle | Chemistry Dai, Xuedong, 1970- Synthesis and applications of atropisomeric quinazolinone phosphine ligands |
| title | Synthesis and applications of atropisomeric quinazolinone phosphine ligands |
| title_full | Synthesis and applications of atropisomeric quinazolinone phosphine ligands |
| title_fullStr | Synthesis and applications of atropisomeric quinazolinone phosphine ligands |
| title_full_unstemmed | Synthesis and applications of atropisomeric quinazolinone phosphine ligands |
| title_short | Synthesis and applications of atropisomeric quinazolinone phosphine ligands |
| title_sort | synthesis and applications of atropisomeric quinazolinone phosphine ligands |
| topic | Chemistry |
| url | http://hdl.handle.net/1721.1/47887 |
| work_keys_str_mv | AT daixuedong1970 synthesisandapplicationsofatropisomericquinazolinonephosphineligands |