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



Tashenov, Yerbolat, Daniels, Mathias, Robeyns, Koen, Van Meervelt, Luc ORCID: 0000-0003-2186-5209, Dehaen, Wim, Suleimen, Yerlan M and Szakonyi, Zsolt
(2018) Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol. MOLECULES, 23 (4). E771-.

Access the full-text of this item by clicking on the Open Access link.
[thumbnail of Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol.pdf] Text
Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol.pdf - Published version

Download (2MB) | Preview

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.

Item Type: Article
Uncontrolled Keywords: sabinol, terpenoid, catalyst, chiral ligand, triol, aminodiol, asymmetric catalysis
Depositing User: Symplectic Admin
Date Deposited: 04 Jun 2019 10:12
Last Modified: 19 Jan 2023 00:41
DOI: 10.3390/molecules23040771
Open Access URL: https://doi.org/10.3390/molecules23040771
Related URLs:
URI: https://livrepository.liverpool.ac.uk/id/eprint/3044381