Nickel-catalyzed asymmetric transfer hydrogenation of unsaturated C=C and C=N bonds using formic acid
This thesis describes my work on nickel-catalyzed asymmetric transfer hydrogenation of unsaturated C=C and C=N bonds using formic acid. It contains three main parts. Chapter one reports a highly enantioselective asymmetric hydrogenation of hydrazones with a chiral ligand, (S)-Binapine. Both aryl an...
| Հիմնական հեղինակ: | |
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| Այլ հեղինակներ: | |
| Ձևաչափ: | Թեզիս |
| Լեզու: | English |
| Հրապարակվել է: |
2017
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| Խորագրեր: | |
| Առցանց հասանելիություն: | http://hdl.handle.net/10356/72337 |
| _version_ | 1826124460813451264 |
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| author | Xu, Haiyan |
| author2 | Steve Zhou |
| author_facet | Steve Zhou Xu, Haiyan |
| author_sort | Xu, Haiyan |
| collection | NTU |
| description | This thesis describes my work on nickel-catalyzed asymmetric transfer hydrogenation of unsaturated C=C and C=N bonds using formic acid. It contains three main parts.
Chapter one reports a highly enantioselective asymmetric hydrogenation of hydrazones with a chiral ligand, (S)-Binapine. Both aryl and aliphatic methyl hydrazones afforded the desired products in good to excellent ee values. Furthermore, DFT calculation revealed that the nickel catalyst controls the asymmetric hydride insertion to unsaturated C=N bonds by controlling the binding conformation of the amide directing group, instead of differentiating group on the imine fragment.
Chapter two describes asymmetric reductive amination of simple ketones with sulfonamides in one pot. With a nickel/(S)-Binapine catalytic system, a series of chiral tosylamines were obtained in high enantioselectivities. This one-pot reductive amination of simple ketones is operationally simple and avoids the isolation and purification of the intermediate tosylimines.
Chapter three reports the asymmetric hydrogenation of olefins for the synthesis of unnatural amino acid derivatives, using a nickel catalyst ligated by a chiral bisphosphine (S)-Binapine. In some cases of cyclic tetra-substituted dehydroamino acid derivatives, good yields and excellent ee values were achieved. |
| first_indexed | 2024-10-01T06:21:00Z |
| format | Thesis |
| id | ntu-10356/72337 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T06:21:00Z |
| publishDate | 2017 |
| record_format | dspace |
| spelling | ntu-10356/723372023-02-28T23:49:28Z Nickel-catalyzed asymmetric transfer hydrogenation of unsaturated C=C and C=N bonds using formic acid Xu, Haiyan Steve Zhou School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Organic chemistry This thesis describes my work on nickel-catalyzed asymmetric transfer hydrogenation of unsaturated C=C and C=N bonds using formic acid. It contains three main parts. Chapter one reports a highly enantioselective asymmetric hydrogenation of hydrazones with a chiral ligand, (S)-Binapine. Both aryl and aliphatic methyl hydrazones afforded the desired products in good to excellent ee values. Furthermore, DFT calculation revealed that the nickel catalyst controls the asymmetric hydride insertion to unsaturated C=N bonds by controlling the binding conformation of the amide directing group, instead of differentiating group on the imine fragment. Chapter two describes asymmetric reductive amination of simple ketones with sulfonamides in one pot. With a nickel/(S)-Binapine catalytic system, a series of chiral tosylamines were obtained in high enantioselectivities. This one-pot reductive amination of simple ketones is operationally simple and avoids the isolation and purification of the intermediate tosylimines. Chapter three reports the asymmetric hydrogenation of olefins for the synthesis of unnatural amino acid derivatives, using a nickel catalyst ligated by a chiral bisphosphine (S)-Binapine. In some cases of cyclic tetra-substituted dehydroamino acid derivatives, good yields and excellent ee values were achieved. Doctor of Philosophy (SPMS) 2017-06-08T02:48:08Z 2017-06-08T02:48:08Z 2017 Thesis Xu, H. (2017). Nickel-catalyzed asymmetric transfer hydrogenation of unsaturated C=C and C=N bonds using formic acid. Doctoral thesis, Nanyang Technological University, Singapore. http://hdl.handle.net/10356/72337 10.32657/10356/72337 en 196 p. application/pdf |
| spellingShingle | DRNTU::Science::Chemistry::Organic chemistry Xu, Haiyan Nickel-catalyzed asymmetric transfer hydrogenation of unsaturated C=C and C=N bonds using formic acid |
| title | Nickel-catalyzed asymmetric transfer hydrogenation of unsaturated C=C and C=N bonds using formic acid |
| title_full | Nickel-catalyzed asymmetric transfer hydrogenation of unsaturated C=C and C=N bonds using formic acid |
| title_fullStr | Nickel-catalyzed asymmetric transfer hydrogenation of unsaturated C=C and C=N bonds using formic acid |
| title_full_unstemmed | Nickel-catalyzed asymmetric transfer hydrogenation of unsaturated C=C and C=N bonds using formic acid |
| title_short | Nickel-catalyzed asymmetric transfer hydrogenation of unsaturated C=C and C=N bonds using formic acid |
| title_sort | nickel catalyzed asymmetric transfer hydrogenation of unsaturated c c and c n bonds using formic acid |
| topic | DRNTU::Science::Chemistry::Organic chemistry |
| url | http://hdl.handle.net/10356/72337 |
| work_keys_str_mv | AT xuhaiyan nickelcatalyzedasymmetrictransferhydrogenationofunsaturatedccandcnbondsusingformicacid |