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Molecules 2018, 23(4), 771; https://doi.org/10.3390/molecules23040771

Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol

1
Institute of Applied Chemistry, Chemistry Department of L.N. Gumilyov Eurasian National University, Munaitpassov st., 5, 010008 Astana, Kazakhstan
2
KU Leuven, Department of Chemistry, Celestijnenlaan 200F, B-3001 Leuven, Belgium
3
IMCN, Molecules Solids and Reactivity division (MOST), Université catholique de Louvain, Place Pasteur 1, B-1348 Louvain-la-Neuve, Belgium
4
Institute of Pharmaceutical Chemistry, University of Szeged, Eötvös u. 6, H-6720 Szeged, Hungary
5
Interdisciplinary Centre of Natural Products, University of Szeged, H 6720 Szeged, Hungary
*
Author to whom correspondence should be addressed.
Academic Editors: Prof. Dr. Laura Palombi and Prof. Dr. Antonio Massa
Received: 13 February 2018 / Revised: 21 March 2018 / Accepted: 22 March 2018 / Published: 27 March 2018
(This article belongs to the Special Issue Enantioselective Catalysis)
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Abstract

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. View Full-Text
Keywords: sabinol; terpenoid; catalyst; chiral ligand; triol; aminodiol; asymmetric catalysis sabinol; terpenoid; catalyst; chiral ligand; triol; aminodiol; asymmetric catalysis
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Tashenov, Y.; Daniels, M.; Robeyns, K.; Van Meervelt, L.; Dehaen, W.; Suleimen, Y.M.; Szakonyi, Z. Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol. Molecules 2018, 23, 771.

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