Regioselective heck reaction of aliphatic olefins
The thesis presents selective Heck reaction of terminal aliphatic olefins. Previously, the reaction used to give a complex mixture of isomers. The first part is about Heck reaction of aliphatic olefins using aryl triflates. A new ferrocene bisphosphine dnpf was developed to give high internal regios...
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| Other Authors: | |
| Format: | Thesis |
| Language: | English |
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2014
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| Online Access: | https://hdl.handle.net/10356/55334 |
| _version_ | 1811676471283941376 |
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| author | Qin, Liena |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Qin, Liena |
| author_sort | Qin, Liena |
| collection | NTU |
| description | The thesis presents selective Heck reaction of terminal aliphatic olefins. Previously, the reaction used to give a complex mixture of isomers. The first part is about Heck reaction of aliphatic olefins using aryl triflates. A new ferrocene bisphosphine dnpf was developed to give high internal regioselectivity. The ligand dnpf is now commercialized by Sigma-Aldrich. Our experimental and DFT studies indicated that the bulky dnpf ligand disfavored terminal insertion via steric effect. The second part is about selective Heck reaction of alphatic olefins using aryl bromides and chlorides. The method can also be applied to styrenes. The selectivity was again controlled by dnpf. Methanol solvent and acidic additive n-Bu3NHCl were needed to to promote halide dissociation from neutral aryl palladium complexes via hydrogen bonding. DFT calculation of halide dissociation indicated that hydrogen bonding by methanol and ammonium salt with bromide affected halide dissociation both thermodynamically and kinetically. |
| first_indexed | 2024-10-01T02:22:00Z |
| format | Thesis |
| id | ntu-10356/55334 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T02:22:00Z |
| publishDate | 2014 |
| record_format | dspace |
| spelling | ntu-10356/553342023-02-28T23:31:48Z Regioselective heck reaction of aliphatic olefins Qin, Liena School of Physical and Mathematical Sciences Zhou Jianrong DRNTU::Science::Chemistry::Organic chemistry The thesis presents selective Heck reaction of terminal aliphatic olefins. Previously, the reaction used to give a complex mixture of isomers. The first part is about Heck reaction of aliphatic olefins using aryl triflates. A new ferrocene bisphosphine dnpf was developed to give high internal regioselectivity. The ligand dnpf is now commercialized by Sigma-Aldrich. Our experimental and DFT studies indicated that the bulky dnpf ligand disfavored terminal insertion via steric effect. The second part is about selective Heck reaction of alphatic olefins using aryl bromides and chlorides. The method can also be applied to styrenes. The selectivity was again controlled by dnpf. Methanol solvent and acidic additive n-Bu3NHCl were needed to to promote halide dissociation from neutral aryl palladium complexes via hydrogen bonding. DFT calculation of halide dissociation indicated that hydrogen bonding by methanol and ammonium salt with bromide affected halide dissociation both thermodynamically and kinetically. DOCTOR OF PHILOSOPHY (SPMS) 2014-02-11T04:24:08Z 2014-02-11T04:24:08Z 2014 2014 Thesis Qin, L. (2014). Regioselective heck reaction of aliphatic olefins. Doctoral thesis, Nanyang Technological University, Singapore. https://hdl.handle.net/10356/55334 10.32657/10356/55334 en 226 p. application/pdf |
| spellingShingle | DRNTU::Science::Chemistry::Organic chemistry Qin, Liena Regioselective heck reaction of aliphatic olefins |
| title | Regioselective heck reaction of aliphatic olefins |
| title_full | Regioselective heck reaction of aliphatic olefins |
| title_fullStr | Regioselective heck reaction of aliphatic olefins |
| title_full_unstemmed | Regioselective heck reaction of aliphatic olefins |
| title_short | Regioselective heck reaction of aliphatic olefins |
| title_sort | regioselective heck reaction of aliphatic olefins |
| topic | DRNTU::Science::Chemistry::Organic chemistry |
| url | https://hdl.handle.net/10356/55334 |
| work_keys_str_mv | AT qinliena regioselectiveheckreactionofaliphaticolefins |