Full metadata record
| DC Field | Value | Language |
|---|---|---|
| dc.contributor | Department of Applied Biology and Chemical Technology | en_US |
| dc.contributor.advisor | Kwong, Fuk Yee (ABCT) | - |
| dc.creator | Wong, Shun Man | - |
| dc.identifier.uri | https://theses.lib.polyu.edu.hk/handle/200/7898 | - |
| dc.language | English | en_US |
| dc.publisher | Hong Kong Polytechnic University | - |
| dc.rights | All rights reserved | en_US |
| dc.title | Design and synthesis of hemilabile heterocyclic phosphine Ligands and their applications in palladium-catalyzed carbon-carbon and carbon-nitrogen bond-construction processes | en_US |
| dcterms.abstract | A new family of hemilabile benzimidazolyl phosphine ligands was designed and synthesized. The benzimidazole scaffold of this family of ligands could be easily prepared and diversified from inexpensive substituted o-phenylenediamines and substituted carboxylic acids by conventional Phillips benzimidazole synthesis. Two classes of ligands, P,N-type 2-arylated benzimidazolyl phosphine ligands and alterable P,O-or P,N-type 2-phosphino-substituted benzimidazolyl ligands, were successfully synthesized by a “Cross-matching approach. The 2-arylated benzimidazolyl phosphine ligands showed excellent catalytic activities for the Suzuki-Miyaura coupling of aryl chlorides with arylboronic acids, especially under very-low-catalyst-loading down to 1 ppm. In addition, these ligands were efficient towards Suzuki-Miyaura coupling of aryl chlorides with potassium aryltrifluoroborates. Notably, the X-ray crystallographic data confirmed that the ligand was coordinated in a κ2-P,N fashion to the palladium center. On the other hand, the palladium complexes of 2-phosphino-substituted benzimidazolyl ligands showed coordination in a κ2-P,N fashion and potential P,O-hemilabile ability, which could be altered by tuning the steric bulkiness of phosphino group. Interestingly, the complexes with P,O-coordination and P,N-coordination showed high efficacy towards Suzuki-Miyaura coupling and Buchwald-Hartwig amination of aryl chlorides, respectively. Particularly noteworthy, to probe with these fascinating hemilabile properties, chemoselective cross-coupling of aryl chlorides was also examined. The palladium-ligand complexes showed essentially complete orthogonal property (>99%) to afford Suzuki coupling products when carrying out competitive cross-coupling of aryl chlorides with arylboronic acids and amines. | en_US |
| dcterms.extent | 1 volume (various pagings) : illustrations ; 30 cm | en_US |
| dcterms.isPartOf | PolyU Electronic Theses | en_US |
| dcterms.issued | 2015 | en_US |
| dcterms.educationalLevel | All Doctorate | en_US |
| dcterms.educationalLevel | Ph.D. | en_US |
| dcterms.LCSH | Phosphorus compounds. | en_US |
| dcterms.LCSH | Ligands (Biochemistry) | en_US |
| dcterms.LCSH | Catalysis. | en_US |
| dcterms.LCSH | Hong Kong Polytechnic University -- Dissertations | en_US |
| dcterms.accessRights | open access | en_US |
Files in This Item:
| File | Description | Size | Format | |
|---|---|---|---|---|
| b27981848.pdf | For All Users | 21.28 MB | Adobe PDF | View/Open |
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