Copper-catalyzed C-SI bond formation based on SI-B bond activation
This thesis describes copper-catalyzed carbon-silicon bond formations, including 1,4-addition to α,β-unsaturated esters, 1,2-addition to aldehydes and highly regioselective silylcupration of terminal alkynes, based on Si-B bond activation. A brief summary of traditional Si-B bond activation catalyze...
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| Format: | Thesis |
| Language: | English |
| Published: |
2011
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| Online Access: | https://hdl.handle.net/10356/44605 |
| _version_ | 1811677306285981696 |
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| author | Peng, Wang |
| author2 | Loh Teck Peng |
| author_facet | Loh Teck Peng Peng, Wang |
| author_sort | Peng, Wang |
| collection | NTU |
| description | This thesis describes copper-catalyzed carbon-silicon bond formations, including 1,4-addition to α,β-unsaturated esters, 1,2-addition to aldehydes and highly regioselective silylcupration of terminal alkynes, based on Si-B bond activation. A brief summary of traditional Si-B bond activation catalyzed by transition metal catalysts is given. Some recent examples of silylboration of terminal alkynes and unsaturated carbonyl compounds are highlighted in this chapter. The mechanisms involving Si-B bond activation of above reactions are also thoroughly discussed.
A highly efficient β-silylation of α,β-unsaturated esters catalyzed by an N-heterocyclic carbene-copper complex based on Si-B bond activation has been developed. This new method produced highly functionalized products with a wide substrate scope, thus providing an ideal strategy to asymmetric transformations. A new protocol to prepare α-hydroxysilanes using an N-heterocyclic carbene copper(I) complex as catalyst has been developed and successfully applied to the addition to various aldehydes in good yields under ambient conditions. This is the first successful example to realize catalytic nucleophilic transfer of silicon to aldehydes through a Cu-Si intermediate based on Si-B bond activation. |
| first_indexed | 2024-10-01T02:35:16Z |
| format | Thesis |
| id | ntu-10356/44605 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T02:35:16Z |
| publishDate | 2011 |
| record_format | dspace |
| spelling | ntu-10356/446052023-02-28T23:32:40Z Copper-catalyzed C-SI bond formation based on SI-B bond activation Peng, Wang Loh Teck Peng School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Organic chemistry::Organic synthesis This thesis describes copper-catalyzed carbon-silicon bond formations, including 1,4-addition to α,β-unsaturated esters, 1,2-addition to aldehydes and highly regioselective silylcupration of terminal alkynes, based on Si-B bond activation. A brief summary of traditional Si-B bond activation catalyzed by transition metal catalysts is given. Some recent examples of silylboration of terminal alkynes and unsaturated carbonyl compounds are highlighted in this chapter. The mechanisms involving Si-B bond activation of above reactions are also thoroughly discussed. A highly efficient β-silylation of α,β-unsaturated esters catalyzed by an N-heterocyclic carbene-copper complex based on Si-B bond activation has been developed. This new method produced highly functionalized products with a wide substrate scope, thus providing an ideal strategy to asymmetric transformations. A new protocol to prepare α-hydroxysilanes using an N-heterocyclic carbene copper(I) complex as catalyst has been developed and successfully applied to the addition to various aldehydes in good yields under ambient conditions. This is the first successful example to realize catalytic nucleophilic transfer of silicon to aldehydes through a Cu-Si intermediate based on Si-B bond activation. DOCTOR OF PHILOSOPHY (SPMS) 2011-06-02T07:50:33Z 2011-06-02T07:50:33Z 2011 2011 Thesis Peng, W. (2011). Copper-catalyzed C-SI bond formation based on SI-B bond activation. Doctoral thesis, Nanyang Technological University, Singapore. https://hdl.handle.net/10356/44605 10.32657/10356/44605 en 122 p. application/pdf |
| spellingShingle | DRNTU::Science::Chemistry::Organic chemistry::Organic synthesis Peng, Wang Copper-catalyzed C-SI bond formation based on SI-B bond activation |
| title | Copper-catalyzed C-SI bond formation based on SI-B bond activation |
| title_full | Copper-catalyzed C-SI bond formation based on SI-B bond activation |
| title_fullStr | Copper-catalyzed C-SI bond formation based on SI-B bond activation |
| title_full_unstemmed | Copper-catalyzed C-SI bond formation based on SI-B bond activation |
| title_short | Copper-catalyzed C-SI bond formation based on SI-B bond activation |
| title_sort | copper catalyzed c si bond formation based on si b bond activation |
| topic | DRNTU::Science::Chemistry::Organic chemistry::Organic synthesis |
| url | https://hdl.handle.net/10356/44605 |
| work_keys_str_mv | AT pengwang coppercatalyzedcsibondformationbasedonsibbondactivation |