Aminophosphine Palladium Pincer Complexes for Suzuki and Heck Reactions
The aminophosphine-based pincer complexes [C6H3-2,6-{NHP(piperidinyl)2}2Pd(Cl)] (2) and [C6H3-2,6-{OP(piperidinyl)2}2Pd(Cl)] (3) are readily prepared from cheap starting materials by sequential addition of 1,1?,1?-phosphinetriyltripiperidine and 1,3-diaminobenzene or resorcinol to solution...
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| Format: | Article |
| Language: | deu |
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Swiss Chemical Society
2009-02-01
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| Series: | CHIMIA |
| Subjects: | |
| Online Access: | https://www.chimia.ch/chimia/article/view/4604 |
| _version_ | 1818282421437595648 |
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| author | Jeanne L. Bolliger Christian M. Frech |
| author_facet | Jeanne L. Bolliger Christian M. Frech |
| author_sort | Jeanne L. Bolliger |
| collection | DOAJ |
| description |
The aminophosphine-based pincer complexes [C6H3-2,6-{NHP(piperidinyl)2}2Pd(Cl)] (2) and [C6H3-2,6-{OP(piperidinyl)2}2Pd(Cl)] (3) are readily prepared from cheap starting materials by
sequential addition of 1,1?,1?-phosphinetriyltripiperidine and 1,3-diaminobenzene or resorcinol to solutions of [Pd(cod)(Cl)2] (cod = cyclooctadiene) in toluene under N2 in 'one pot'. Compounds 2 and 3 proved to be not only excellent catalysts
for the Suzuki and the Heck cross-coupling reactions, but they are also very convenient to use: The toluene solutions of the 'one-pot' syntheses can be used directly for the catalytic reactions, thereby saving the time-consuming isolation of the catalysts. The Suzuki cross-coupling reaction
catalyzed by 2 and 3 can be performed in air at 100 °C in toluene of technical quality: in the presence of only 0.001mol% of catalyst, several electronically deactivated and sterically hindered aryl bromides are quantitatively coupled with phenylboronic acid within a few
minutes of reaction time. Furthermore, complex 2 enables the use of activated and non-activated aryl chlorides as coupling partners in the Suzuki reaction. Compounds 2 and 3 have also been shown to be highly active and reliable Heck catalysts: Very low catalyst loadings
and short reaction times are required for the quantitative coupling of several electronically deactivated and sterically hindered aryl bromides with various olefins at 140 °C. At increased temperatures, even electronically deactivated and sterically hindered aryl chlorides can be efficiently
coupled with olefins in the presence of only 0.01 mol% of catalyst.
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| first_indexed | 2024-12-13T00:20:45Z |
| format | Article |
| id | doaj.art-1a1504e5a73549dcbb4c01fb46634c86 |
| institution | Directory Open Access Journal |
| issn | 0009-4293 2673-2424 |
| language | deu |
| last_indexed | 2024-12-13T00:20:45Z |
| publishDate | 2009-02-01 |
| publisher | Swiss Chemical Society |
| record_format | Article |
| series | CHIMIA |
| spelling | doaj.art-1a1504e5a73549dcbb4c01fb46634c862022-12-22T00:05:35ZdeuSwiss Chemical SocietyCHIMIA0009-42932673-24242009-02-01631-210.2533/chimia.2009.23Aminophosphine Palladium Pincer Complexes for Suzuki and Heck ReactionsJeanne L. BolligerChristian M. Frech The aminophosphine-based pincer complexes [C6H3-2,6-{NHP(piperidinyl)2}2Pd(Cl)] (2) and [C6H3-2,6-{OP(piperidinyl)2}2Pd(Cl)] (3) are readily prepared from cheap starting materials by sequential addition of 1,1?,1?-phosphinetriyltripiperidine and 1,3-diaminobenzene or resorcinol to solutions of [Pd(cod)(Cl)2] (cod = cyclooctadiene) in toluene under N2 in 'one pot'. Compounds 2 and 3 proved to be not only excellent catalysts for the Suzuki and the Heck cross-coupling reactions, but they are also very convenient to use: The toluene solutions of the 'one-pot' syntheses can be used directly for the catalytic reactions, thereby saving the time-consuming isolation of the catalysts. The Suzuki cross-coupling reaction catalyzed by 2 and 3 can be performed in air at 100 °C in toluene of technical quality: in the presence of only 0.001mol% of catalyst, several electronically deactivated and sterically hindered aryl bromides are quantitatively coupled with phenylboronic acid within a few minutes of reaction time. Furthermore, complex 2 enables the use of activated and non-activated aryl chlorides as coupling partners in the Suzuki reaction. Compounds 2 and 3 have also been shown to be highly active and reliable Heck catalysts: Very low catalyst loadings and short reaction times are required for the quantitative coupling of several electronically deactivated and sterically hindered aryl bromides with various olefins at 140 °C. At increased temperatures, even electronically deactivated and sterically hindered aryl chlorides can be efficiently coupled with olefins in the presence of only 0.01 mol% of catalyst. https://www.chimia.ch/chimia/article/view/4604AminophosphinesC-c couplingHeck reactionPincer complexesSuzuki reaction |
| spellingShingle | Jeanne L. Bolliger Christian M. Frech Aminophosphine Palladium Pincer Complexes for Suzuki and Heck Reactions CHIMIA Aminophosphines C-c coupling Heck reaction Pincer complexes Suzuki reaction |
| title | Aminophosphine Palladium Pincer Complexes for Suzuki and Heck Reactions |
| title_full | Aminophosphine Palladium Pincer Complexes for Suzuki and Heck Reactions |
| title_fullStr | Aminophosphine Palladium Pincer Complexes for Suzuki and Heck Reactions |
| title_full_unstemmed | Aminophosphine Palladium Pincer Complexes for Suzuki and Heck Reactions |
| title_short | Aminophosphine Palladium Pincer Complexes for Suzuki and Heck Reactions |
| title_sort | aminophosphine palladium pincer complexes for suzuki and heck reactions |
| topic | Aminophosphines C-c coupling Heck reaction Pincer complexes Suzuki reaction |
| url | https://www.chimia.ch/chimia/article/view/4604 |
| work_keys_str_mv | AT jeannelbolliger aminophosphinepalladiumpincercomplexesforsuzukiandheckreactions AT christianmfrech aminophosphinepalladiumpincercomplexesforsuzukiandheckreactions |