Stereoselective Transesterification of P‐Chirogenic Hydroxybinaphthyl Phosphinates
Abstract The substitution reaction of phosphinates with a binaphthyloxy group at the phosphorus atom with lithium alkoxides proceeded with good to high efficiencies to give P‐chirogenic phosphinates with a high enantiomeric ratio. As alcohols, primary, secondary, and tertiary alcohols could be used,...
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2022-11-01
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| Series: | ChemistryOpen |
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| Online Access: | https://doi.org/10.1002/open.202100294 |
| _version_ | 1811304191646236672 |
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| author | Akari Kawajiri Dr. Taro Udagawa Prof. Dr. Mao Minoura Prof. Dr. Toshiaki Murai |
| author_facet | Akari Kawajiri Dr. Taro Udagawa Prof. Dr. Mao Minoura Prof. Dr. Toshiaki Murai |
| author_sort | Akari Kawajiri |
| collection | DOAJ |
| description | Abstract The substitution reaction of phosphinates with a binaphthyloxy group at the phosphorus atom with lithium alkoxides proceeded with good to high efficiencies to give P‐chirogenic phosphinates with a high enantiomeric ratio. As alcohols, primary, secondary, and tertiary alcohols could be used, and the use of tert‐butyl alcohol yielded the products with a higher enantiomeric ratio. A substrate with two different alkyl groups on the phosphorus atom could also participate in the substitution reaction to give the corresponding products in good yields with excellent selectivity. The molecular structures of one of the substrates and the corresponding products, determined by X‐ray analyses, proved that the substitution reaction at the phosphorus atom proceeded with inversion of the absolute configuration. The usefulness of the reaction was demonstrated by using it to prepare a drug candidate for Duchenne muscular dystrophy. Finally, thionation of the resulting phosphinates was carried out to form P‐chirogenic phosphinothioates. |
| first_indexed | 2024-04-13T08:02:42Z |
| format | Article |
| id | doaj.art-b9c5a1a50db749e68cb23555a6c6ab6c |
| institution | Directory Open Access Journal |
| issn | 2191-1363 |
| language | English |
| last_indexed | 2024-04-13T08:02:42Z |
| publishDate | 2022-11-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemistryOpen |
| spelling | doaj.art-b9c5a1a50db749e68cb23555a6c6ab6c2022-12-22T02:55:15ZengWiley-VCHChemistryOpen2191-13632022-11-011111n/an/a10.1002/open.202100294Stereoselective Transesterification of P‐Chirogenic Hydroxybinaphthyl PhosphinatesAkari Kawajiri0Dr. Taro Udagawa1Prof. Dr. Mao Minoura2Prof. Dr. Toshiaki Murai3Department 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 JapanDepartment of Chemistry and Biomolecular Science Faculty of Engineering Gifu University Yanagido Gifu 501-1193 JapanAbstract The substitution reaction of phosphinates with a binaphthyloxy group at the phosphorus atom with lithium alkoxides proceeded with good to high efficiencies to give P‐chirogenic phosphinates with a high enantiomeric ratio. As alcohols, primary, secondary, and tertiary alcohols could be used, and the use of tert‐butyl alcohol yielded the products with a higher enantiomeric ratio. A substrate with two different alkyl groups on the phosphorus atom could also participate in the substitution reaction to give the corresponding products in good yields with excellent selectivity. The molecular structures of one of the substrates and the corresponding products, determined by X‐ray analyses, proved that the substitution reaction at the phosphorus atom proceeded with inversion of the absolute configuration. The usefulness of the reaction was demonstrated by using it to prepare a drug candidate for Duchenne muscular dystrophy. Finally, thionation of the resulting phosphinates was carried out to form P‐chirogenic phosphinothioates.https://doi.org/10.1002/open.202100294binaphthyoxy groupchirality transferP-chirogenic phosphinatessubstitution reaction |
| spellingShingle | Akari Kawajiri Dr. Taro Udagawa Prof. Dr. Mao Minoura Prof. Dr. Toshiaki Murai Stereoselective Transesterification of P‐Chirogenic Hydroxybinaphthyl Phosphinates ChemistryOpen binaphthyoxy group chirality transfer P-chirogenic phosphinates substitution reaction |
| title | Stereoselective Transesterification of P‐Chirogenic Hydroxybinaphthyl Phosphinates |
| title_full | Stereoselective Transesterification of P‐Chirogenic Hydroxybinaphthyl Phosphinates |
| title_fullStr | Stereoselective Transesterification of P‐Chirogenic Hydroxybinaphthyl Phosphinates |
| title_full_unstemmed | Stereoselective Transesterification of P‐Chirogenic Hydroxybinaphthyl Phosphinates |
| title_short | Stereoselective Transesterification of P‐Chirogenic Hydroxybinaphthyl Phosphinates |
| title_sort | stereoselective transesterification of p chirogenic hydroxybinaphthyl phosphinates |
| topic | binaphthyoxy group chirality transfer P-chirogenic phosphinates substitution reaction |
| url | https://doi.org/10.1002/open.202100294 |
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