Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization
The addition of interelement compounds with heteroatom-heteroatom single bonds to carbon-carbon unsaturated bonds under light irradiation is believed to be an atomically efficient method to procure materials with carbon-heteroatom bonds. In this study, we achieved the photoinduced bisphosphination o...
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MDPI AG
2022-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/4/1284 |
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| author | Yuki Yamamoto Ryo Tanaka Shintaro Kodama Akihiro Nomoto Akiya Ogawa |
| author_facet | Yuki Yamamoto Ryo Tanaka Shintaro Kodama Akihiro Nomoto Akiya Ogawa |
| author_sort | Yuki Yamamoto |
| collection | DOAJ |
| description | The addition of interelement compounds with heteroatom-heteroatom single bonds to carbon-carbon unsaturated bonds under light irradiation is believed to be an atomically efficient method to procure materials with carbon-heteroatom bonds. In this study, we achieved the photoinduced bisphosphination of alkynes using the phosphorus interelement compound, tetraphenyldiphosphine monosulfide (<b>1</b>), to stereoselectively obtain the corresponding (<i>E</i>)-<i>vic</i>-1,2-bisphosphinoalkenes, which are important transition-metal ligands. The bisphosphination reaction was performed by mixing <b>1</b> and various alkynes and then exposing the mixture to light irradiation. Optimization of the conditions for the bisphosphination reaction resulted in a wide substrate range and excellent <i>trans</i>-selectivity. Moreover, the completely regioselective introduction of pentavalent and trivalent phosphorus groups to the terminal and internal positions of the alkynes, respectively, was achieved. We also found that the novel double-bond isomerization reaction of the synthesized bisphosphinated products occurred with a catalytic amount of a base under mild conditions. Our method for the photoinduced bisphosphination of carbon-carbon unsaturated compounds may have strong implications for both organic synthesis and organometallic and catalyst chemistry. |
| first_indexed | 2024-03-09T21:20:26Z |
| format | Article |
| id | doaj.art-0b836bb605c34b758f91b342e97fbb62 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T21:20:26Z |
| publishDate | 2022-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-0b836bb605c34b758f91b342e97fbb622023-11-23T21:21:35ZengMDPI AGMolecules1420-30492022-02-01274128410.3390/molecules27041284Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond IsomerizationYuki Yamamoto0Ryo Tanaka1Shintaro Kodama2Akihiro Nomoto3Akiya Ogawa4Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Osaka 599-8531, JapanDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Osaka 599-8531, JapanDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Osaka 599-8531, JapanDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Osaka 599-8531, JapanDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Osaka 599-8531, JapanThe addition of interelement compounds with heteroatom-heteroatom single bonds to carbon-carbon unsaturated bonds under light irradiation is believed to be an atomically efficient method to procure materials with carbon-heteroatom bonds. In this study, we achieved the photoinduced bisphosphination of alkynes using the phosphorus interelement compound, tetraphenyldiphosphine monosulfide (<b>1</b>), to stereoselectively obtain the corresponding (<i>E</i>)-<i>vic</i>-1,2-bisphosphinoalkenes, which are important transition-metal ligands. The bisphosphination reaction was performed by mixing <b>1</b> and various alkynes and then exposing the mixture to light irradiation. Optimization of the conditions for the bisphosphination reaction resulted in a wide substrate range and excellent <i>trans</i>-selectivity. Moreover, the completely regioselective introduction of pentavalent and trivalent phosphorus groups to the terminal and internal positions of the alkynes, respectively, was achieved. We also found that the novel double-bond isomerization reaction of the synthesized bisphosphinated products occurred with a catalytic amount of a base under mild conditions. Our method for the photoinduced bisphosphination of carbon-carbon unsaturated compounds may have strong implications for both organic synthesis and organometallic and catalyst chemistry.https://www.mdpi.com/1420-3049/27/4/1284interelement compoundsphotoinduced bisphosphinationradical reactionstereoselective synthesisdouble-bond isomerization |
| spellingShingle | Yuki Yamamoto Ryo Tanaka Shintaro Kodama Akihiro Nomoto Akiya Ogawa Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization Molecules interelement compounds photoinduced bisphosphination radical reaction stereoselective synthesis double-bond isomerization |
| title | Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization |
| title_full | Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization |
| title_fullStr | Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization |
| title_full_unstemmed | Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization |
| title_short | Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization |
| title_sort | photoinduced bisphosphination of alkynes with phosphorus interelement compounds and its application to double bond isomerization |
| topic | interelement compounds photoinduced bisphosphination radical reaction stereoselective synthesis double-bond isomerization |
| url | https://www.mdpi.com/1420-3049/27/4/1284 |
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