Rhodium-catalyzed 1,4-addition of triorgano(vinyl)silanes to electron-deficient olefins and application towards the preparation of functionalized organoboron compounds
It was recently discovered in the author’s group that the transmetalation of typically unreactive triorgano(vinyl)silanes could be accomplished with [RhCl(CO)2]2, leading to the development of a rhodium-catalyzed acylation of triorgano(vinyl)silanes with acid anhydrides. Employing a similar transm...
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| Other Authors: | |
| Format: | Thesis |
| Language: | English |
| Published: |
2010
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| Online Access: | http://hdl.handle.net/10356/20874 |
| _version_ | 1826110450306121728 |
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| author | Ng, Yu Rui |
| author2 | Koichi Narasaka |
| author_facet | Koichi Narasaka Ng, Yu Rui |
| author_sort | Ng, Yu Rui |
| collection | NTU |
| description | It was recently discovered in the author’s group that the transmetalation of typically
unreactive triorgano(vinyl)silanes could be accomplished with [RhCl(CO)2]2, leading to the development of a rhodium-catalyzed acylation of triorgano(vinyl)silanes with acid anhydrides.
Employing a similar transmetalat
ion, a catalytic 1,4-addition of triorgano(vinyl)silanes with various electron deficient olefins was developed by the use of [RhCl(CO)2]2. This is the first example of the 1,4-addition of tetraorganosilicon compounds in the absence of any activating functional groups. This reaction was found to be tolerant towards vinylsilanes with different substitution patterns.
In order to investigate the reactivities of the carbon-boron and carbon-silicon bonds
towards [RhCl(CO)2]2, alkenyl compounds having both organometallic bonds were applied in [RhCl(CO)2]2 catalyzed acylation and 1,4-addition reactions. It was found that the carbon-silicon bond could be selectively cleaved, thereby retaining only the boranyl group. This led to the synthesis of acylated and alkylated organoboron compounds, which were previously difficult to
synthesize. |
| first_indexed | 2024-10-01T02:34:36Z |
| format | Thesis |
| id | ntu-10356/20874 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T02:34:36Z |
| publishDate | 2010 |
| record_format | dspace |
| spelling | ntu-10356/208742023-02-28T23:32:38Z Rhodium-catalyzed 1,4-addition of triorgano(vinyl)silanes to electron-deficient olefins and application towards the preparation of functionalized organoboron compounds Ng, Yu Rui Koichi Narasaka School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds It was recently discovered in the author’s group that the transmetalation of typically unreactive triorgano(vinyl)silanes could be accomplished with [RhCl(CO)2]2, leading to the development of a rhodium-catalyzed acylation of triorgano(vinyl)silanes with acid anhydrides. Employing a similar transmetalat ion, a catalytic 1,4-addition of triorgano(vinyl)silanes with various electron deficient olefins was developed by the use of [RhCl(CO)2]2. This is the first example of the 1,4-addition of tetraorganosilicon compounds in the absence of any activating functional groups. This reaction was found to be tolerant towards vinylsilanes with different substitution patterns. In order to investigate the reactivities of the carbon-boron and carbon-silicon bonds towards [RhCl(CO)2]2, alkenyl compounds having both organometallic bonds were applied in [RhCl(CO)2]2 catalyzed acylation and 1,4-addition reactions. It was found that the carbon-silicon bond could be selectively cleaved, thereby retaining only the boranyl group. This led to the synthesis of acylated and alkylated organoboron compounds, which were previously difficult to synthesize. Master of Science 2010-02-25T09:14:47Z 2010-02-25T09:14:47Z 2010 2010 Thesis http://hdl.handle.net/10356/20874 en 108 p. application/pdf |
| spellingShingle | DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds Ng, Yu Rui Rhodium-catalyzed 1,4-addition of triorgano(vinyl)silanes to electron-deficient olefins and application towards the preparation of functionalized organoboron compounds |
| title | Rhodium-catalyzed 1,4-addition of triorgano(vinyl)silanes to electron-deficient olefins and application towards the preparation of functionalized organoboron compounds |
| title_full | Rhodium-catalyzed 1,4-addition of triorgano(vinyl)silanes to electron-deficient olefins and application towards the preparation of functionalized organoboron compounds |
| title_fullStr | Rhodium-catalyzed 1,4-addition of triorgano(vinyl)silanes to electron-deficient olefins and application towards the preparation of functionalized organoboron compounds |
| title_full_unstemmed | Rhodium-catalyzed 1,4-addition of triorgano(vinyl)silanes to electron-deficient olefins and application towards the preparation of functionalized organoboron compounds |
| title_short | Rhodium-catalyzed 1,4-addition of triorgano(vinyl)silanes to electron-deficient olefins and application towards the preparation of functionalized organoboron compounds |
| title_sort | rhodium catalyzed 1 4 addition of triorgano vinyl silanes to electron deficient olefins and application towards the preparation of functionalized organoboron compounds |
| topic | DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds |
| url | http://hdl.handle.net/10356/20874 |
| work_keys_str_mv | AT ngyurui rhodiumcatalyzed14additionoftriorganovinylsilanestoelectrondeficientolefinsandapplicationtowardsthepreparationoffunctionalizedorganoboroncompounds |