Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/85322
DC FieldValueLanguage
dc.contributorDepartment of Applied Biology and Chemical Technology-
dc.creatorWong, Shun Man-
dc.identifier.urihttps://theses.lib.polyu.edu.hk/handle/200/7898-
dc.language.isoEnglish-
dc.titleDesign and synthesis of hemilabile heterocyclic phosphine Ligands and their applications in palladium-catalyzed carbon-carbon and carbon-nitrogen bond-construction processes-
dc.typeThesis-
dcterms.abstractA 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.-
dcterms.accessRightsopen access-
dcterms.educationLevelPh.D.-
dcterms.extent1 volume (various pagings) : illustrations ; 30 cm-
dcterms.issued2015-
dcterms.LCSHPhosphorus compounds.-
dcterms.LCSHLigands (Biochemistry)-
dcterms.LCSHCatalysis.-
dcterms.LCSHHong Kong Polytechnic University -- Dissertations-
Appears in Collections:Thesis
Show simple item record

Page views

6
Citations as of Jun 26, 2022

Google ScholarTM

Check


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.