1. Recent Development for Stereoselective Synthesis of 1,3-Polyol Ye Zhu Prof. Burgess’ Group Aug. 19, 2010

2. 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.

3. Introduction Michael, Muller, et al, Synthesis, 2006, 557.

4. C-C Bond Forming Reactions Introduction Asymmetric Alkylation Knochel, P., et al, Tetrahedron Lett., 1993, 5881.

5. C-C Bond Forming Reactions Introduction Asymmetric Allylation Leighton, J.L. et al, Angew. Chem. Int. Ed. 2003, 946. advantage: allylation can be carried out iteratively easily

6. C-C Bond Forming Reactions Introduction Reagent Controlled Aldol Reaction Mahler, U., et al, Chem. Ber. 1988, 2035.

7. Stereoselective Reduction Introduction Directed Reduction of β-Hydroxyketones

8. Stereoselective Reduction Introduction Asymmetric Hydrogenation Uchida Y.. et al, Tetrahedron 1993, 1997.

9. Homoallylic Alcohol As Substrate Introduction Asymmetric Silylformylation Leighton, J.L. et al, J. Am. Chem. Soc. 2000, 122, 8587.

10. Catalytic Asymmetric Overman Esterification Kirsch, S.F., et al, Org. Lett., 2009, 5634. Overman, L.E.; et al, J. Am. Chem. Soc. 2005, 2866.Kirsch, S.F., et al, Chem. Commun.., 2007, 4164.

11. 1,3-anti-Diols Through Catalytic Hydrogenations Genet J.P., et al, Org. Lett., 2007, 105.

12. Iterative Cr-Mediated Catalytic Asymmetric Allylation Kishi, Y., et al, Org. Lett., 2008, 3073. Kishi, Y., et al, Org. Lett., 2008, 3077.

13. Iterative Cr-Mediated Catalytic Asymmetric Allylation Kishi, Y., et al, Org. Lett., 2008, 3073. Kishi, Y., et al, Org. Lett., 2008, 3077.

14. Proline-Catalyzed Sequential α- Aminoxylation and Horner-Wadsworth- Emmons Olefination of Aldehydes Kumar, P., et al, Org. Lett., 2009, 2611.

15. Iridium-Catalyzed Enantioselective Carbonyl Allylation and Iterative Two- Directional Assembly of 1,3-Polyols Krische, M. J. et al, Angew. Chem. Int. Ed., 2009, 5018.

16. 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.

17. 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.

18. Elongation of 1,3-Polyols via Iterative Catalyst-Directed Carbonyl Allylation from the Alcohol Oxidation Level

19. Iridium-Catalyzed Enantioselective Carbonyl Allylation and Iterative Two- Directional Assembly of 1,3-Polyols Krische, M. J. et al, Angew. Chem. Int. Ed., 2009, 5018.

20. Iridium-Catalyzed Enantioselective Carbonyl Allylation and Iterative Two- Directional Assembly of 1,3-Polyols Krische, M. J. et al, Angew. Chem. Int. Ed., 2009, 5018.

21. 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.

22. 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.

23. STEREOCHEMISTRY OF ALTERNATING POLYOL CHAINS: 13C NMR ANALYSIS OF 1,3-DIOL ACETONIDES Rycbnovsky, S.D., et al, Tetrahedron Lett., 1990, 945

26. Thanks