A new method for the synthesis of α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues
A convenient approach has been developed to α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues by α-phosphonylation, α-phosphinylation or α-phosphinoylation of 1-(N-acylamino)alkylphosphonates, that, in turn, are easily accessible from N-...
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2015-08-01
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| Series: | Beilstein Journal of Organic Chemistry |
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| Online Access: | https://doi.org/10.3762/bjoc.11.153 |
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| author | Anna Kuźnik Roman Mazurkiewicz Mirosława Grymel Katarzyna Zielińska Jakub Adamek Ewa Chmielewska Marta Bochno Sonia Kubica |
| author_facet | Anna Kuźnik Roman Mazurkiewicz Mirosława Grymel Katarzyna Zielińska Jakub Adamek Ewa Chmielewska Marta Bochno Sonia Kubica |
| author_sort | Anna Kuźnik |
| collection | DOAJ |
| description | A convenient approach has been developed to α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues by α-phosphonylation, α-phosphinylation or α-phosphinoylation of 1-(N-acylamino)alkylphosphonates, that, in turn, are easily accessible from N-acyl-α-amino acids. Effective electrophilic activation of the α-position of 1-(N-acetylamino)alkylphosphonates was achieved by electrochemical α-methoxylation of these compounds in methanol, mediated with NaCl, followed by displacement of the methoxy group with triphenylphosphonium tetrafluoroborate to give hitherto unknown 1-(N-acetylamino)-1-triphenylphosphoniumalkylphosphonate tetrafluoroborates. The latter compounds react smoothly with trialkyl phosphites, dialkyl phosphonites or alkyl phosphinites in the presence of Hünig’s base and methyltriphenylphosphonium iodide in a Michaelis–Arbuzov-like reaction to give the expected alkylidenebisphosphonates, 1-phosphinylalkylphosphonates or 1-phosphinoylalkylphosphonates, respectively, in good yields. |
| first_indexed | 2024-12-19T23:58:04Z |
| format | Article |
| id | doaj.art-5d169af806ba433ebbefc0a4de6c3794 |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-19T23:58:04Z |
| publishDate | 2015-08-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-5d169af806ba433ebbefc0a4de6c37942022-12-21T20:00:57ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972015-08-011111418142410.3762/bjoc.11.1531860-5397-11-153A new method for the synthesis of α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analoguesAnna Kuźnik0Roman Mazurkiewicz1Mirosława Grymel2Katarzyna Zielińska3Jakub Adamek4Ewa Chmielewska5Marta Bochno6Sonia Kubica7Department of Organic Chemistry, Biochemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, PolandDepartment of Organic Chemistry, Biochemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, PolandDepartment of Organic Chemistry, Biochemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, PolandDepartment of Organic Chemistry, Biochemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, PolandDepartment of Organic Chemistry, Biochemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, PolandDepartment of Bioorganic Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, PolandDepartment of Bioorganic Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, PolandDepartment of Organic Chemistry, Biochemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, PolandA convenient approach has been developed to α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues by α-phosphonylation, α-phosphinylation or α-phosphinoylation of 1-(N-acylamino)alkylphosphonates, that, in turn, are easily accessible from N-acyl-α-amino acids. Effective electrophilic activation of the α-position of 1-(N-acetylamino)alkylphosphonates was achieved by electrochemical α-methoxylation of these compounds in methanol, mediated with NaCl, followed by displacement of the methoxy group with triphenylphosphonium tetrafluoroborate to give hitherto unknown 1-(N-acetylamino)-1-triphenylphosphoniumalkylphosphonate tetrafluoroborates. The latter compounds react smoothly with trialkyl phosphites, dialkyl phosphonites or alkyl phosphinites in the presence of Hünig’s base and methyltriphenylphosphonium iodide in a Michaelis–Arbuzov-like reaction to give the expected alkylidenebisphosphonates, 1-phosphinylalkylphosphonates or 1-phosphinoylalkylphosphonates, respectively, in good yields.https://doi.org/10.3762/bjoc.11.153alkylidenebisphosphonateα-amino acid phosphorus analogueselectrochemical α-methoxylation1-phosphinoylalkylphosphonate1-phosphinylalkylphosphonate |
| spellingShingle | Anna Kuźnik Roman Mazurkiewicz Mirosława Grymel Katarzyna Zielińska Jakub Adamek Ewa Chmielewska Marta Bochno Sonia Kubica A new method for the synthesis of α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues Beilstein Journal of Organic Chemistry alkylidenebisphosphonate α-amino acid phosphorus analogues electrochemical α-methoxylation 1-phosphinoylalkylphosphonate 1-phosphinylalkylphosphonate |
| title | A new method for the synthesis of α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues |
| title_full | A new method for the synthesis of α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues |
| title_fullStr | A new method for the synthesis of α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues |
| title_full_unstemmed | A new method for the synthesis of α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues |
| title_short | A new method for the synthesis of α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues |
| title_sort | new method for the synthesis of α aminoalkylidenebisphosphonates and their asymmetric phosphonyl phosphinyl and phosphonyl phosphinoyl analogues |
| topic | alkylidenebisphosphonate α-amino acid phosphorus analogues electrochemical α-methoxylation 1-phosphinoylalkylphosphonate 1-phosphinylalkylphosphonate |
| url | https://doi.org/10.3762/bjoc.11.153 |
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