Recent Development for
Stereoselective Synthesis of
1,3-Polyol
Ye Zhu
Prof. Burgess’ Group
Aug. 19, 2010
Introduction
The 1,3-polyol structure cluster is present in numerous natural
products ranging from antibiotics to marine natural products. A substructure
search with SciFinder gave 87 and 35 natural products bearing one or more
of 1,3,5,7,9-pentaol(s) and 1,3,5,7,9,11,13-heptaol(s), respectively.
Introduction
Michael, Muller, et al, Synthesis, 2006, 557.
Introduction
C-C Bond Forming Reactions
Asymmetric Alkylation
Knochel, P., et al, Tetrahedron Lett., 1993, 5881.
Introduction
C-C Bond Forming Reactions
Asymmetric Allylation
advantage: allylation can be carried out iteratively easily
Leighton, J.L. et al, Angew. Chem. Int. Ed. 2003, 946.
Introduction
C-C Bond Forming Reactions
Reagent Controlled Aldol Reaction
Mahler, U., et al, Chem. Ber. 1988, 2035.
Introduction
Stereoselective Reduction
Directed Reduction of β-Hydroxyketones
Introduction
Stereoselective Reduction
Asymmetric Hydrogenation
Uchida Y.. et al, Tetrahedron 1993, 1997.
Introduction
Homoallylic Alcohol As Substrate
Asymmetric Silylformylation
Leighton, J.L. et al, J. Am. Chem. Soc. 2000, 122, 8587.
Catalytic Asymmetric Overman
Esterification
Overman, L.E.; et al, J. Am. Chem. Soc. 2005, 2866.
Kirsch, S.F., et al, Chem. Commun.., 2007, 4164.
Kirsch, S.F., et al, Chem. Commun.., 2007, 4164.
Kirsch, S.F., et al, Org. Lett., 2009, 5634.
1,3-anti-Diols Through
Catalytic Hydrogenations
Genet J.P., et al, Org. Lett., 2007, 105.
Iterative Cr-Mediated Catalytic
Asymmetric Allylation
Kishi, Y., et al, Org. Lett., 2008, 3073.
Kishi, Y., et al, Org. Lett., 2008, 3077.
Iterative Cr-Mediated Catalytic
Asymmetric Allylation
Kishi, Y., et al, Org. Lett., 2008, 3073.
Kishi, Y., et al, Org. Lett., 2008, 3077.
Proline-Catalyzed Sequential αAminoxylation and Horner-WadsworthEmmons Olefination of Aldehydes
Kumar, P., et al, Org. Lett., 2009, 2611.
Iridium-Catalyzed Enantioselective
Carbonyl Allylation and Iterative TwoDirectional Assembly of 1,3-Polyols
Krische, M. J. et al, Angew. Chem. Int. Ed., 2009, 5018.
Elongation of 1,3-Polyols via Iterative
Catalyst-Directed Carbonyl Allylation
from the Alcohol Oxidation Level
Krische, M. J. et al, Org. Lett., 2009, 3112.
Elongation of 1,3-Polyols via Iterative
Catalyst-Directed Carbonyl Allylation
from the Alcohol Oxidation Level
Krische, M. J. et al, Org. Lett., 2009, 3112.
Elongation of 1,3-Polyols via Iterative
Catalyst-Directed Carbonyl Allylation
from the Alcohol Oxidation Level
Iridium-Catalyzed Enantioselective
Carbonyl Allylation and Iterative TwoDirectional Assembly of 1,3-Polyols
Krische, M. J. et al, Angew. Chem. Int. Ed., 2009, 5018.
Iridium-Catalyzed Enantioselective
Carbonyl Allylation and Iterative TwoDirectional Assembly of 1,3-Polyols
Krische, M. J. et al, Angew. Chem. Int. Ed., 2009, 5018.
Direct Catalytic Asymmetric Aldol Reactions
of Thioamides: Toward a Stereocontrolled
Synthesis of 1,3-Polyols
Shibasaki, M. et al, J. Am. Chem.Soc., 2009, 18244.
Direct Catalytic Asymmetric Aldol Reactions
of Thioamides: Toward a Stereocontrolled
Synthesis of 1,3-Polyols
Shibasaki, M. et al, J. Am. Chem.Soc., 2009, 18244.
STEREOCHEMISTRY OF ALTERNATING
POLYOL CHAINS: 13C NMR ANALYSIS
OF 1,3-DIOL ACETONIDES
Rycbnovsky, S.D., et al, Tetrahedron Lett., 1990, 945
Rycbnovsky, S.D., et al, Tetrahedron Lett., 1990, 945
Thanks