Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes
Organophosphorus compounds with stereogenic phosphorus and carbon atoms have received increasing attention. In this regards, primary phosphines with a stereogenic carbon atom adjacent to the phosphorus atom were synthesized by the reduction in phosphonates and phosphonoselenoates with a binaphthyl g...
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MDPI AG
2021-11-01
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| Online Access: | https://www.mdpi.com/2673-401X/2/4/23 |
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| author | Toshiaki Murai Ryota Wada Kouji Iwata Yuuki Maekawa Kazuma Kuwabara Mao Minoura |
| author_facet | Toshiaki Murai Ryota Wada Kouji Iwata Yuuki Maekawa Kazuma Kuwabara Mao Minoura |
| author_sort | Toshiaki Murai |
| collection | DOAJ |
| description | Organophosphorus compounds with stereogenic phosphorus and carbon atoms have received increasing attention. In this regards, primary phosphines with a stereogenic carbon atom adjacent to the phosphorus atom were synthesized by the reduction in phosphonates and phosphonoselenoates with a binaphthyl group. Their oxidized products, i.e., phosphine oxides with a stereogenic tetrasubstituted carbon atom, were found to undergo BEt<sub>3</sub>-mediated radical addition to cyclohexene to give <i>P</i>-stereogenic secondary phosphine oxides with a diastereoselectivity of 91:9. The products were characterized by ordinary analytical methods, such as Fourier transform infrared spectroscopy; <sup>1</sup>H, <sup>13</sup>C, and <sup>31</sup>P NMR spectroscopies; and mass spectroscopy. Computational studies on the phosphorus-centered radical species and the obtained product implied that the thermodynamically stable radical and the adduct may be formed as a major diastereomer. The radical addition to a range of alkenes took place in an anti-Markovnikov fashion to give <i>P</i>-stereogenic secondary phosphine oxides. A variety of functional groups in the alkenes were tolerated under the reaction conditions to afford secondary phosphine oxides in moderate yields. Primary phosphines with an alkenyl group, which were generated in situ, underwent intramolecular cyclization to give five- and six-membered cyclic phosphines in high yields after protection by BH<sub>3</sub>. |
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| language | English |
| last_indexed | 2024-03-10T03:22:26Z |
| publishDate | 2021-11-01 |
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| series | Organics |
| spelling | doaj.art-69671a93e2124182be0351f3271eae7f2023-11-23T10:00:01ZengMDPI AGOrganics2673-401X2021-11-012439540310.3390/org2040023Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to AlkenesToshiaki Murai0Ryota Wada1Kouji Iwata2Yuuki Maekawa3Kazuma Kuwabara4Mao Minoura5Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, JapanDepartment of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, JapanDepartment of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, JapanDepartment of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, JapanDepartment of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, JapanDepartment of Chemistry, College of Science, Rikkyo University, Nishi-ikebukuro, Toshima-ku, Tokyo 171-8501, JapanOrganophosphorus compounds with stereogenic phosphorus and carbon atoms have received increasing attention. In this regards, primary phosphines with a stereogenic carbon atom adjacent to the phosphorus atom were synthesized by the reduction in phosphonates and phosphonoselenoates with a binaphthyl group. Their oxidized products, i.e., phosphine oxides with a stereogenic tetrasubstituted carbon atom, were found to undergo BEt<sub>3</sub>-mediated radical addition to cyclohexene to give <i>P</i>-stereogenic secondary phosphine oxides with a diastereoselectivity of 91:9. The products were characterized by ordinary analytical methods, such as Fourier transform infrared spectroscopy; <sup>1</sup>H, <sup>13</sup>C, and <sup>31</sup>P NMR spectroscopies; and mass spectroscopy. Computational studies on the phosphorus-centered radical species and the obtained product implied that the thermodynamically stable radical and the adduct may be formed as a major diastereomer. The radical addition to a range of alkenes took place in an anti-Markovnikov fashion to give <i>P</i>-stereogenic secondary phosphine oxides. A variety of functional groups in the alkenes were tolerated under the reaction conditions to afford secondary phosphine oxides in moderate yields. Primary phosphines with an alkenyl group, which were generated in situ, underwent intramolecular cyclization to give five- and six-membered cyclic phosphines in high yields after protection by BH<sub>3</sub>.https://www.mdpi.com/2673-401X/2/4/23anti-Markovnikov radical additionfive- and six-membered cyclic phosphinesprimary phosphine oxidesprimary phosphines |
| spellingShingle | Toshiaki Murai Ryota Wada Kouji Iwata Yuuki Maekawa Kazuma Kuwabara Mao Minoura Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes Organics anti-Markovnikov radical addition five- and six-membered cyclic phosphines primary phosphine oxides primary phosphines |
| title | Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes |
| title_full | Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes |
| title_fullStr | Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes |
| title_full_unstemmed | Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes |
| title_short | Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes |
| title_sort | primary phosphines and phosphine oxides with a stereogenic carbon center adjacent to the phosphorus atom synthesis and anti markovnikov radical addition to alkenes |
| topic | anti-Markovnikov radical addition five- and six-membered cyclic phosphines primary phosphine oxides primary phosphines |
| url | https://www.mdpi.com/2673-401X/2/4/23 |
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