Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol
A library of bidentate diols, as well as tridentate triols and aminodiols, derived from (+)-sabinol, was synthesized in a stereoselective manner. Sabinol was transformed into allylic trichloroacetamide via Overman rearrangement of the corresponding trichloroacetimidate. After changing the protecting...
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MDPI AG
2018-03-01
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| Series: | Molecules |
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| Online Access: | http://www.mdpi.com/1420-3049/23/4/771 |
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| author | Yerbolat Tashenov Mathias Daniels Koen Robeyns Luc Van Meervelt Wim Dehaen Yerlan M. Suleimen Zsolt Szakonyi |
| author_facet | Yerbolat Tashenov Mathias Daniels Koen Robeyns Luc Van Meervelt Wim Dehaen Yerlan M. Suleimen Zsolt Szakonyi |
| author_sort | Yerbolat Tashenov |
| collection | DOAJ |
| description | A library of bidentate diols, as well as tridentate triols and aminodiols, derived from (+)-sabinol, was synthesized in a stereoselective manner. Sabinol was transformed into allylic trichloroacetamide via Overman rearrangement of the corresponding trichloroacetimidate. After changing the protecting group to Boc, the enamine was subjected to stereospecific dihydroxylation with OsO4/NMO, resulting in the (1R,2R,3R,5R)-aminodiol diastereomer. The obtained primary aminodiol was transformed to a secondary analogue. The ring closure of the N-benzyl-substituted aminodiol with formaldehyde was investigated and regioselective formation of the spiro-oxazolidine ring was observed. Hydroboration or dihydroxylation of sabinol or its benzyl ether with OsO4/NMO resulted in the formation of sabinane-based diols and triols following a highly stereospecific reaction. Treatment of sabinol with m-CPBA afforded O-benzoyl triol as a diastereoisomer of the directly dihydroxylated product, instead of the expected epoxy alcohol. The resulting aminodiols, diol, and triols were applied as chiral catalysts in the reaction of diethylzinc and benzaldehyde from moderate to good selectivity. |
| first_indexed | 2024-04-13T02:15:27Z |
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| id | doaj.art-face16e405a147d49a42f21de6add6c0 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-04-13T02:15:27Z |
| publishDate | 2018-03-01 |
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| record_format | Article |
| series | Molecules |
| spelling | doaj.art-face16e405a147d49a42f21de6add6c02022-12-22T03:07:10ZengMDPI AGMolecules1420-30492018-03-0123477110.3390/molecules23040771molecules23040771Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-SabinolYerbolat Tashenov0Mathias Daniels1Koen Robeyns2Luc Van Meervelt3Wim Dehaen4Yerlan M. Suleimen5Zsolt Szakonyi6Institute of Applied Chemistry, Chemistry Department of L.N. Gumilyov Eurasian National University, Munaitpassov st., 5, 010008 Astana, KazakhstanKU Leuven, Department of Chemistry, Celestijnenlaan 200F, B-3001 Leuven, BelgiumIMCN, Molecules Solids and Reactivity division (MOST), Université catholique de Louvain, Place Pasteur 1, B-1348 Louvain-la-Neuve, BelgiumKU Leuven, Department of Chemistry, Celestijnenlaan 200F, B-3001 Leuven, BelgiumKU Leuven, Department of Chemistry, Celestijnenlaan 200F, B-3001 Leuven, BelgiumInstitute of Applied Chemistry, Chemistry Department of L.N. Gumilyov Eurasian National University, Munaitpassov st., 5, 010008 Astana, KazakhstanInstitute of Pharmaceutical Chemistry, University of Szeged, Eötvös u. 6, H-6720 Szeged, HungaryA library of bidentate diols, as well as tridentate triols and aminodiols, derived from (+)-sabinol, was synthesized in a stereoselective manner. Sabinol was transformed into allylic trichloroacetamide via Overman rearrangement of the corresponding trichloroacetimidate. After changing the protecting group to Boc, the enamine was subjected to stereospecific dihydroxylation with OsO4/NMO, resulting in the (1R,2R,3R,5R)-aminodiol diastereomer. The obtained primary aminodiol was transformed to a secondary analogue. The ring closure of the N-benzyl-substituted aminodiol with formaldehyde was investigated and regioselective formation of the spiro-oxazolidine ring was observed. Hydroboration or dihydroxylation of sabinol or its benzyl ether with OsO4/NMO resulted in the formation of sabinane-based diols and triols following a highly stereospecific reaction. Treatment of sabinol with m-CPBA afforded O-benzoyl triol as a diastereoisomer of the directly dihydroxylated product, instead of the expected epoxy alcohol. The resulting aminodiols, diol, and triols were applied as chiral catalysts in the reaction of diethylzinc and benzaldehyde from moderate to good selectivity.http://www.mdpi.com/1420-3049/23/4/771sabinolterpenoidcatalystchiral ligandtriolaminodiolasymmetric catalysis |
| spellingShingle | Yerbolat Tashenov Mathias Daniels Koen Robeyns Luc Van Meervelt Wim Dehaen Yerlan M. Suleimen Zsolt Szakonyi Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol Molecules sabinol terpenoid catalyst chiral ligand triol aminodiol asymmetric catalysis |
| title | Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol |
| title_full | Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol |
| title_fullStr | Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol |
| title_full_unstemmed | Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol |
| title_short | Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol |
| title_sort | stereoselective syntheses and application of chiral bi and tridentate ligands derived from sabinol |
| topic | sabinol terpenoid catalyst chiral ligand triol aminodiol asymmetric catalysis |
| url | http://www.mdpi.com/1420-3049/23/4/771 |
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