Chiral imine copper chloride-catalyzed enantioselective desymmetrization of 2-substituted 1,2,3-propanetriols
- 30 January 2007
- journal article
- Published by Proceedings of the National Academy of Sciences in Proceedings of the National Academy of Sciences of the United States of America
- Vol. 104 (5), 1471-1475
- https://doi.org/10.1073/pnas.0607865104
Abstract
Catalytic enantioselective desymmetrization of meso-2-substituted glycerols has been developed to secure a novel synthetic route to chiral tertiary alcohols. The transformation has been realized by monobenzoylation using benzoyl chloride and triethylamine in the presence of the imine ligand (25)-CuCl2 complex in THF at ambient temperature. The desymmetrization turned out to be greatly dependent on acylating reagent, base, solvent, and needless to say, catalyst. Extensive screening of chiral ligands led us to combine bromopyridinecarboxaldehyde 1 and phenyloxazoline amine 12 derived from tert-leucine, the bromo and phenyl substituents of which proved to be indispensable. All of the substrates have been desymmetrized to the corresponding monobenzoates with high enantioselectivity up to 96% enantiomeric excess. The catalytic system allows broad structural diversity of substrates and its synthetic versatility has been demonstrated by an efficient synthetic route to a known key precursor 68 of triazole antifungals.Keywords
This publication has 97 references indexed in Scilit:
- Annelid phylogeny and the status of Sipuncula and EchiuraBMC Evolutionary Biology, 2007
- Naked corals: Skeleton loss in ScleractiniaProceedings of the National Academy of Sciences of the United States of America, 2006
- Lophotrochozoan mitochondrial genomesIntegrative and Comparative Biology, 2006
- ProtTest: selection of best-fit models of protein evolutionBioinformatics, 2005
- Mitochondrial Genomes of Clymenella torquata (Maldanidae) and Riftia pachyptila (Siboglinidae): Evidence for Conserved Gene Order in AnnelidaMolecular Biology and Evolution, 2004
- Early Cambrian sipunculan worms from southwest ChinaProceedings Of The Royal Society B-Biological Sciences, 2004
- Metameric organisation of the nervous system in developmental stages of Urechis caupo (Echiura) and its phylogenetic implicationsZoomorphology, 2002
- Are Echiura derived from a segmented ancestor? Immunohistochemical analysis of the nervous system in developmental stages of Bonellia viridisJournal of Morphology, 2002
- Analysis of the complete mitochondrial DNA sequence of the brachiopod Terebratulina retusa places Brachiopoda within the protostomesProceedings Of The Royal Society B-Biological Sciences, 1999
- The larval ocelli of Golfingia misakiana (Sipuncula, Golfingiidae) and of a pelagosphera of another unidentified speciesZoomorphology, 1997