Stereoselective Synthesis and Investigation of Isopulegol-Based Chiral Ligands
A library of isopulegol-based bi-, tri- and tetrafunctional chiral ligands has been developed from commercially available (−)-isopulegol and applied as chiral catalysts in the addition of diethylzinc to benzaldehyde. Michael addition of primary amines towards <i>α</i>-...
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MDPI AG
2019-08-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/20/16/4050 |
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| author | Tam Minh Le Tamás Szilasi Bettina Volford András Szekeres Ferenc Fülöp Zsolt Szakonyi |
| author_facet | Tam Minh Le Tamás Szilasi Bettina Volford András Szekeres Ferenc Fülöp Zsolt Szakonyi |
| author_sort | Tam Minh Le |
| collection | DOAJ |
| description | A library of isopulegol-based bi-, tri- and tetrafunctional chiral ligands has been developed from commercially available (−)-isopulegol and applied as chiral catalysts in the addition of diethylzinc to benzaldehyde. Michael addition of primary amines towards <i>α</i>-methylene-<i>γ</i>-butyrolactone, followed by reduction, was accomplished to provide aminodiols in highly stereoselective transformations. Stereoselective epoxidation of (+)-neoisopulegol, derived from natural (−)-isopulegol, and subsequent oxirane ring opening with primary amines afforded aminodiols. The regioselective ring closure of <i>N</i>-substituted aminodiols with formaldehyde was also investigated. Hydroxylation of (+)-neoisopulegol resulted in diol, which was then transformed into aminotriols by aminolysis of its epoxides. Dihydroxylation of (+)-neoisopulegol or derivatives with OsO<sub>4</sub>/NMO gave neoisopulegol-based di-, tri- and tetraols in highly stereoselective reactions. The antimicrobial activity of aminodiol and aminotriol derivatives as well as di-, tri- and tetraols was also explored. In addition, structure−activity relationships were examined by assessing substituent effects on the aminodiol and aminotriol systems. |
| first_indexed | 2024-04-13T00:15:56Z |
| format | Article |
| id | doaj.art-818eccd912f049a796248a3c8a813dd3 |
| institution | Directory Open Access Journal |
| issn | 1422-0067 |
| language | English |
| last_indexed | 2024-04-13T00:15:56Z |
| publishDate | 2019-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-818eccd912f049a796248a3c8a813dd32022-12-22T03:10:57ZengMDPI AGInternational Journal of Molecular Sciences1422-00672019-08-012016405010.3390/ijms20164050ijms20164050Stereoselective Synthesis and Investigation of Isopulegol-Based Chiral LigandsTam Minh Le0Tamás Szilasi1Bettina Volford2András Szekeres3Ferenc Fülöp4Zsolt Szakonyi5Institute of Pharmaceutical Chemistry, University of Szeged, Interdisciplinary excellent center, H-6720 Szeged, Eötvös utca 6, HungaryInstitute of Pharmaceutical Chemistry, University of Szeged, Interdisciplinary excellent center, H-6720 Szeged, Eötvös utca 6, HungaryDepartment of Microbiology, University of Szeged, 6726 Szeged, Közép fasor 52, HungaryDepartment of Microbiology, University of Szeged, 6726 Szeged, Közép fasor 52, HungaryInstitute of Pharmaceutical Chemistry, University of Szeged, Interdisciplinary excellent center, H-6720 Szeged, Eötvös utca 6, HungaryInstitute of Pharmaceutical Chemistry, University of Szeged, Interdisciplinary excellent center, H-6720 Szeged, Eötvös utca 6, HungaryA library of isopulegol-based bi-, tri- and tetrafunctional chiral ligands has been developed from commercially available (−)-isopulegol and applied as chiral catalysts in the addition of diethylzinc to benzaldehyde. Michael addition of primary amines towards <i>α</i>-methylene-<i>γ</i>-butyrolactone, followed by reduction, was accomplished to provide aminodiols in highly stereoselective transformations. Stereoselective epoxidation of (+)-neoisopulegol, derived from natural (−)-isopulegol, and subsequent oxirane ring opening with primary amines afforded aminodiols. The regioselective ring closure of <i>N</i>-substituted aminodiols with formaldehyde was also investigated. Hydroxylation of (+)-neoisopulegol resulted in diol, which was then transformed into aminotriols by aminolysis of its epoxides. Dihydroxylation of (+)-neoisopulegol or derivatives with OsO<sub>4</sub>/NMO gave neoisopulegol-based di-, tri- and tetraols in highly stereoselective reactions. The antimicrobial activity of aminodiol and aminotriol derivatives as well as di-, tri- and tetraols was also explored. In addition, structure−activity relationships were examined by assessing substituent effects on the aminodiol and aminotriol systems.https://www.mdpi.com/1422-0067/20/16/4050aminodiolsaminotriolsdiolstriolstetraolschiral catalystsantimicrobial activity |
| spellingShingle | Tam Minh Le Tamás Szilasi Bettina Volford András Szekeres Ferenc Fülöp Zsolt Szakonyi Stereoselective Synthesis and Investigation of Isopulegol-Based Chiral Ligands International Journal of Molecular Sciences aminodiols aminotriols diols triols tetraols chiral catalysts antimicrobial activity |
| title | Stereoselective Synthesis and Investigation of Isopulegol-Based Chiral Ligands |
| title_full | Stereoselective Synthesis and Investigation of Isopulegol-Based Chiral Ligands |
| title_fullStr | Stereoselective Synthesis and Investigation of Isopulegol-Based Chiral Ligands |
| title_full_unstemmed | Stereoselective Synthesis and Investigation of Isopulegol-Based Chiral Ligands |
| title_short | Stereoselective Synthesis and Investigation of Isopulegol-Based Chiral Ligands |
| title_sort | stereoselective synthesis and investigation of isopulegol based chiral ligands |
| topic | aminodiols aminotriols diols triols tetraols chiral catalysts antimicrobial activity |
| url | https://www.mdpi.com/1422-0067/20/16/4050 |
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