Asymmetric synthesis of cyano- functionalised-1, 3-diphosphine via organopalladium promoted hydrophosphination reaction.
The asymmetric hydrophosphination reaction involving (Triphenylphosphoranylidene)acetonitrile and diphenylphosphine was carried out by utilizing palladium complex containing ortho-metalated (R)-(dimethylamino)ethyl)naphthalene as the chiral auxiliary. The cyano-functionalized monophosphine substr...
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| Other Authors: | |
| Format: | Final Year Project (FYP) |
| Language: | English |
| Published: |
2010
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| Online Access: | http://hdl.handle.net/10356/40654 |
| _version_ | 1811683237917884416 |
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| author | Lee, Zhi Yi. |
| author2 | Leung Pak Hing |
| author_facet | Leung Pak Hing Lee, Zhi Yi. |
| author_sort | Lee, Zhi Yi. |
| collection | NTU |
| description | The asymmetric hydrophosphination reaction involving
(Triphenylphosphoranylidene)acetonitrile and diphenylphosphine was carried out by utilizing
palladium complex containing ortho-metalated (R)-(dimethylamino)ethyl)naphthalene as the
chiral auxiliary. The cyano-functionalized monophosphine substrate were synthesized from 3-
chloro-1,1-diethoxypropane via a versatile one-pot process. Subsequent hydrophosphination of
coordinated cyano-functionalized phosphine substrates promoted by the chiral auxillary gave
corresponding functionalized 1, 3-diphosphine product. Functional group transformation of the
cyano group to formyl group was performed by selective reduction of diphosphine palladium
complex by using DIBAL-H. The reaction proceeded regiospecifically and stereospecifically to
give the corresponding formyl-functionalised 1, 3-diphosphine products. The coordination
properties and absolute configurations of the novel formyl-functionalized 1, 3-diphosphine complexes were established by single crystal X-ray crystallography. The enantiomerically pure
formyl functionalized diphosphine ligand could be subsequently liberated stereospecifically by
treatment of the corresponding dichloro palladium complexes with aqueous potassium cyanide in
high yield. |
| first_indexed | 2024-10-01T04:09:33Z |
| format | Final Year Project (FYP) |
| id | ntu-10356/40654 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T04:09:33Z |
| publishDate | 2010 |
| record_format | dspace |
| spelling | ntu-10356/406542023-02-28T23:13:21Z Asymmetric synthesis of cyano- functionalised-1, 3-diphosphine via organopalladium promoted hydrophosphination reaction. Lee, Zhi Yi. Leung Pak Hing School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Organic chemistry::Organic synthesis The asymmetric hydrophosphination reaction involving (Triphenylphosphoranylidene)acetonitrile and diphenylphosphine was carried out by utilizing palladium complex containing ortho-metalated (R)-(dimethylamino)ethyl)naphthalene as the chiral auxiliary. The cyano-functionalized monophosphine substrate were synthesized from 3- chloro-1,1-diethoxypropane via a versatile one-pot process. Subsequent hydrophosphination of coordinated cyano-functionalized phosphine substrates promoted by the chiral auxillary gave corresponding functionalized 1, 3-diphosphine product. Functional group transformation of the cyano group to formyl group was performed by selective reduction of diphosphine palladium complex by using DIBAL-H. The reaction proceeded regiospecifically and stereospecifically to give the corresponding formyl-functionalised 1, 3-diphosphine products. The coordination properties and absolute configurations of the novel formyl-functionalized 1, 3-diphosphine complexes were established by single crystal X-ray crystallography. The enantiomerically pure formyl functionalized diphosphine ligand could be subsequently liberated stereospecifically by treatment of the corresponding dichloro palladium complexes with aqueous potassium cyanide in high yield. Bachelor of Science in Chemistry and Biological Chemistry 2010-06-17T06:11:01Z 2010-06-17T06:11:01Z 2010 2010 Final Year Project (FYP) http://hdl.handle.net/10356/40654 en 30 p. application/pdf |
| spellingShingle | DRNTU::Science::Chemistry::Organic chemistry::Organic synthesis Lee, Zhi Yi. Asymmetric synthesis of cyano- functionalised-1, 3-diphosphine via organopalladium promoted hydrophosphination reaction. |
| title | Asymmetric synthesis of cyano- functionalised-1, 3-diphosphine via organopalladium promoted hydrophosphination reaction. |
| title_full | Asymmetric synthesis of cyano- functionalised-1, 3-diphosphine via organopalladium promoted hydrophosphination reaction. |
| title_fullStr | Asymmetric synthesis of cyano- functionalised-1, 3-diphosphine via organopalladium promoted hydrophosphination reaction. |
| title_full_unstemmed | Asymmetric synthesis of cyano- functionalised-1, 3-diphosphine via organopalladium promoted hydrophosphination reaction. |
| title_short | Asymmetric synthesis of cyano- functionalised-1, 3-diphosphine via organopalladium promoted hydrophosphination reaction. |
| title_sort | asymmetric synthesis of cyano functionalised 1 3 diphosphine via organopalladium promoted hydrophosphination reaction |
| topic | DRNTU::Science::Chemistry::Organic chemistry::Organic synthesis |
| url | http://hdl.handle.net/10356/40654 |
| work_keys_str_mv | AT leezhiyi asymmetricsynthesisofcyanofunctionalised13diphosphineviaorganopalladiumpromotedhydrophosphinationreaction |