Design, syntheses and applications of chiral transition metal complexes bearing phosphorus-containing ligands
A series of optically active tertiary phosphine compounds were prepared via catalytic asymmetric hydrophosphination of specially designed substrates. The C-stereogenic phosphines obtained were used in the formation of symmetrical PC(aryl)P, unsymmetrical PC(aryl)N and NC(sp3)X (X = O, S) transition...
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| Other Authors: | |
| Format: | Thesis |
| Language: | English |
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2015
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| Online Access: | https://hdl.handle.net/10356/65840 |
| _version_ | 1811677454110031872 |
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| author | Yang, Xiangyuan |
| author2 | Leung Pak Hing |
| author_facet | Leung Pak Hing Yang, Xiangyuan |
| author_sort | Yang, Xiangyuan |
| collection | NTU |
| description | A series of optically active tertiary phosphine compounds were prepared via catalytic asymmetric hydrophosphination of specially designed substrates. The C-stereogenic phosphines obtained were used in the formation of symmetrical PC(aryl)P, unsymmetrical PC(aryl)N and NC(sp3)X (X = O, S) transition metal pincer complexes, as well as novel copper(I) clusters. This work focuses on the syntheses, purification, characterization and application of the pincer complexes in asymmetric transformations such as hydrophosphination reactions. A regio-divergent hydrophosphination protocol involving a judicious choice of chiral phosphine−palladium(II) catalyst was successful in generating either the 1,4- or 1,6-adduct selectively from diunsaturated substrates. Subsequently, detailed investigations of the stereo-control imparted by the pincer architecture allowed the preparation of highly efficient catalysts which provided excellent regio- and stereo-selectivity in the asymmetric conjugate addition of phosphine nucleophiles to activated olefins. |
| first_indexed | 2024-10-01T02:37:37Z |
| format | Thesis |
| id | ntu-10356/65840 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T02:37:37Z |
| publishDate | 2015 |
| record_format | dspace |
| spelling | ntu-10356/658402023-02-28T23:32:49Z Design, syntheses and applications of chiral transition metal complexes bearing phosphorus-containing ligands Yang, Xiangyuan Leung Pak Hing School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Analytical chemistry A series of optically active tertiary phosphine compounds were prepared via catalytic asymmetric hydrophosphination of specially designed substrates. The C-stereogenic phosphines obtained were used in the formation of symmetrical PC(aryl)P, unsymmetrical PC(aryl)N and NC(sp3)X (X = O, S) transition metal pincer complexes, as well as novel copper(I) clusters. This work focuses on the syntheses, purification, characterization and application of the pincer complexes in asymmetric transformations such as hydrophosphination reactions. A regio-divergent hydrophosphination protocol involving a judicious choice of chiral phosphine−palladium(II) catalyst was successful in generating either the 1,4- or 1,6-adduct selectively from diunsaturated substrates. Subsequently, detailed investigations of the stereo-control imparted by the pincer architecture allowed the preparation of highly efficient catalysts which provided excellent regio- and stereo-selectivity in the asymmetric conjugate addition of phosphine nucleophiles to activated olefins. DOCTOR OF PHILOSOPHY (SPMS) 2015-12-23T06:01:56Z 2015-12-23T06:01:56Z 2015 2015 Thesis Yang, X. (2015). Design, syntheses and applications of chiral transition metal complexes bearing phosphorus-containing ligands. Doctoral thesis, Nanyang Technological University, Singapore. https://hdl.handle.net/10356/65840 10.32657/10356/65840 en 270 p. application/pdf |
| spellingShingle | DRNTU::Science::Chemistry::Analytical chemistry Yang, Xiangyuan Design, syntheses and applications of chiral transition metal complexes bearing phosphorus-containing ligands |
| title | Design, syntheses and applications of chiral transition metal complexes bearing phosphorus-containing ligands |
| title_full | Design, syntheses and applications of chiral transition metal complexes bearing phosphorus-containing ligands |
| title_fullStr | Design, syntheses and applications of chiral transition metal complexes bearing phosphorus-containing ligands |
| title_full_unstemmed | Design, syntheses and applications of chiral transition metal complexes bearing phosphorus-containing ligands |
| title_short | Design, syntheses and applications of chiral transition metal complexes bearing phosphorus-containing ligands |
| title_sort | design syntheses and applications of chiral transition metal complexes bearing phosphorus containing ligands |
| topic | DRNTU::Science::Chemistry::Analytical chemistry |
| url | https://hdl.handle.net/10356/65840 |
| work_keys_str_mv | AT yangxiangyuan designsynthesesandapplicationsofchiraltransitionmetalcomplexesbearingphosphoruscontainingligands |