Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation
The nucleophilic addition of methanol and other alcohols to 1,1-diphenylethylene (1) and styrene (6) into the Markovnikov- and anti-Markovnikov-type products was selectively achieved with 1-(N,N-dimethylamino)pyrene (Py) and 1,7-dicyanoperylene-3,4:9,10-tetracarboxylic acid bisimide (PDI) as photore...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2015-04-01
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| Series: | Beilstein Journal of Organic Chemistry |
| Subjects: | |
| Online Access: | https://doi.org/10.3762/bjoc.11.62 |
| _version_ | 1818913549735428096 |
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| author | Martin Weiser Sergej Hermann Alexander Penner Hans-Achim Wagenknecht |
| author_facet | Martin Weiser Sergej Hermann Alexander Penner Hans-Achim Wagenknecht |
| author_sort | Martin Weiser |
| collection | DOAJ |
| description | The nucleophilic addition of methanol and other alcohols to 1,1-diphenylethylene (1) and styrene (6) into the Markovnikov- and anti-Markovnikov-type products was selectively achieved with 1-(N,N-dimethylamino)pyrene (Py) and 1,7-dicyanoperylene-3,4:9,10-tetracarboxylic acid bisimide (PDI) as photoredox catalysts. The regioselectivity was controlled by the photocatalyst. For the reductive mode towards the Markovnikov-type regioselectivity, Py was applied as photocatalyst and triethylamine as electron shuttle. This approach was also used for intramolecular additions. For the oxidative mode towards the anti-Markovnikov-type regioselectivety, PDI was applied together with Ph–SH as additive. Photocatalytic additions of a variety of alcohols gave the corresponding products in good to excellent yields. The proposed photocatalytic electron transfer mechanism was supported by detection of the PDI radical anion as key intermediate and by comparison of two intramolecular reactions with different electron density. Representative mesoflow reactor experiments allowed to significantly shorten the irradiation times and to use sunlight as “green” light source. |
| first_indexed | 2024-12-19T23:32:16Z |
| format | Article |
| id | doaj.art-90db8155397f46a58ca61d0f4dadd935 |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-19T23:32:16Z |
| publishDate | 2015-04-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-90db8155397f46a58ca61d0f4dadd9352022-12-21T20:01:42ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972015-04-0111156857510.3762/bjoc.11.621860-5397-11-62Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientationMartin Weiser0Sergej Hermann1Alexander Penner2Hans-Achim Wagenknecht3Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, GermanyInstitute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, GermanyInstitute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, GermanyInstitute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, GermanyThe nucleophilic addition of methanol and other alcohols to 1,1-diphenylethylene (1) and styrene (6) into the Markovnikov- and anti-Markovnikov-type products was selectively achieved with 1-(N,N-dimethylamino)pyrene (Py) and 1,7-dicyanoperylene-3,4:9,10-tetracarboxylic acid bisimide (PDI) as photoredox catalysts. The regioselectivity was controlled by the photocatalyst. For the reductive mode towards the Markovnikov-type regioselectivity, Py was applied as photocatalyst and triethylamine as electron shuttle. This approach was also used for intramolecular additions. For the oxidative mode towards the anti-Markovnikov-type regioselectivety, PDI was applied together with Ph–SH as additive. Photocatalytic additions of a variety of alcohols gave the corresponding products in good to excellent yields. The proposed photocatalytic electron transfer mechanism was supported by detection of the PDI radical anion as key intermediate and by comparison of two intramolecular reactions with different electron density. Representative mesoflow reactor experiments allowed to significantly shorten the irradiation times and to use sunlight as “green” light source.https://doi.org/10.3762/bjoc.11.62electron transferperylene bisimidephotocatalysisphotochemistrypyrene |
| spellingShingle | Martin Weiser Sergej Hermann Alexander Penner Hans-Achim Wagenknecht Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation Beilstein Journal of Organic Chemistry electron transfer perylene bisimide photocatalysis photochemistry pyrene |
| title | Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation |
| title_full | Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation |
| title_fullStr | Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation |
| title_full_unstemmed | Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation |
| title_short | Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation |
| title_sort | photocatalytic nucleophilic addition of alcohols to styrenes in markovnikov and anti markovnikov orientation |
| topic | electron transfer perylene bisimide photocatalysis photochemistry pyrene |
| url | https://doi.org/10.3762/bjoc.11.62 |
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