New aspects of phosphirene chemistry
Two methodologies have been tested for the functionalization of phosphirenes. In the first one, the C−Si bond of a 2-silylphosphirene is activated by a substoichiometric quantity of fluoride ion (TBAF) in THF at −78 °C. Using this technique, it is possible to perform a protodesilylation or a functio...
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| Format: | Thesis |
| Language: | English |
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2012
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| Online Access: | https://hdl.handle.net/10356/49976 |
| _version_ | 1811692009035923456 |
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| author | Panichakul, Duanghathai |
| author2 | Francois Mathey |
| author_facet | Francois Mathey Panichakul, Duanghathai |
| author_sort | Panichakul, Duanghathai |
| collection | NTU |
| description | Two methodologies have been tested for the functionalization of phosphirenes. In the first one, the C−Si bond of a 2-silylphosphirene is activated by a substoichiometric quantity of fluoride ion (TBAF) in THF at −78 °C. Using this technique, it is possible to perform a protodesilylation or a functionalization by benzaldehyde. However, at room temperature with a stoichiometry of fluoride, a nucleophilic attack takes place at P, leading to a ring-opened fluorophosphine. Stille cross-coupling with a 2-stannylphosphirene in the presence of [PdL2] as a catalyst leads to an alkynylphosphine by [1,3] migration of tin from C to P. Next, special chemistry of 2-aminophosphirene: the reaction of the bulkyynamine PhCCNiPr2 with terminal phosphinidene complexes [R−PW(CO)5], generated from phosphanorbornadiene complex, affords the corresponding phosphirenes (R = Ph, OMe) and the diphosphetene (R = Me). The reaction of this phosphirene with dimethyl acetylenedicarboxylate gives the phosphole resulting from the insertion of the alkyne into the P−C(N) bond and the tetrafunctional arene resulting from [2+2+2] cycloaddition of one alkyne with two phosphirene units. Finally, the reaction of strong Lewis acids with 2-amino-3-phenylphosphirene pentacarbonyltungsten complexes leads to the corresponding 2-amino phosphindoles through the unexpected formation of a bond between phosphorus and one of the ortho carbons of the phenyl ring. |
| first_indexed | 2024-10-01T06:28:58Z |
| format | Thesis |
| id | ntu-10356/49976 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T06:28:58Z |
| publishDate | 2012 |
| record_format | dspace |
| spelling | ntu-10356/499762023-02-28T23:50:33Z New aspects of phosphirene chemistry Panichakul, Duanghathai Francois Mathey School of Physical and Mathematical Sciences DRNTU::Science::Chemistry Two methodologies have been tested for the functionalization of phosphirenes. In the first one, the C−Si bond of a 2-silylphosphirene is activated by a substoichiometric quantity of fluoride ion (TBAF) in THF at −78 °C. Using this technique, it is possible to perform a protodesilylation or a functionalization by benzaldehyde. However, at room temperature with a stoichiometry of fluoride, a nucleophilic attack takes place at P, leading to a ring-opened fluorophosphine. Stille cross-coupling with a 2-stannylphosphirene in the presence of [PdL2] as a catalyst leads to an alkynylphosphine by [1,3] migration of tin from C to P. Next, special chemistry of 2-aminophosphirene: the reaction of the bulkyynamine PhCCNiPr2 with terminal phosphinidene complexes [R−PW(CO)5], generated from phosphanorbornadiene complex, affords the corresponding phosphirenes (R = Ph, OMe) and the diphosphetene (R = Me). The reaction of this phosphirene with dimethyl acetylenedicarboxylate gives the phosphole resulting from the insertion of the alkyne into the P−C(N) bond and the tetrafunctional arene resulting from [2+2+2] cycloaddition of one alkyne with two phosphirene units. Finally, the reaction of strong Lewis acids with 2-amino-3-phenylphosphirene pentacarbonyltungsten complexes leads to the corresponding 2-amino phosphindoles through the unexpected formation of a bond between phosphorus and one of the ortho carbons of the phenyl ring. DOCTOR OF PHILOSOPHY (SPMS) 2012-05-28T03:31:51Z 2012-05-28T03:31:51Z 2012 2012 Thesis Panichakul, D. (2012). New aspects of phosphirene chemistry. Doctoral thesis, Nanyang Technological University, Singapore. https://hdl.handle.net/10356/49976 10.32657/10356/49976 en 135 p. application/pdf |
| spellingShingle | DRNTU::Science::Chemistry Panichakul, Duanghathai New aspects of phosphirene chemistry |
| title | New aspects of phosphirene chemistry |
| title_full | New aspects of phosphirene chemistry |
| title_fullStr | New aspects of phosphirene chemistry |
| title_full_unstemmed | New aspects of phosphirene chemistry |
| title_short | New aspects of phosphirene chemistry |
| title_sort | new aspects of phosphirene chemistry |
| topic | DRNTU::Science::Chemistry |
| url | https://hdl.handle.net/10356/49976 |
| work_keys_str_mv | AT panichakulduanghathai newaspectsofphosphirenechemistry |