Synthesis 2012; 44(20): 3145-3151
DOI: 10.1055/s-0031-1291138
practical synthetic procedures
© Georg Thieme Verlag Stuttgart · New York

Efficient Preparation of 1,3-Diol Derivatives with Three Contiguous Stereocenters by an Enantioselective Direct Aldol–Tishchenko Reaction

Tomonori Ichibakase
Graduate School of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-honmachi, Kumamoto 862-0973, Japan, Fax: +81(96)3627692   Email: [email protected]
,
Makoto Nakajima*
Graduate School of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-honmachi, Kumamoto 862-0973, Japan, Fax: +81(96)3627692   Email: [email protected]
› Author Affiliations
Further Information

Publication History

Received: 29 February 2012

Accepted: 21 March 2012

Publication Date:
29 June 2012 (online)


Abstract

1,3-Diol derivatives with three contiguous stereocenters were efficiently prepared by an enantioselective direct aldol–Tishchenko reaction catalyzed by dilithium 3,3′-diphenylbinaphtholate. The reactions of acyclic ketones as aldol donors gave 1,2-syn-1,3-anti-diol derivatives, whereas the reactions of cyclic ketones as aldol donors gave 1,2-anti-1,3-anti-diol derivatives. Sequential aldol–aldol–Tishchenko reactions gave a triol derivative with five consecutive chiral centers.

 
  • References

    • 1a Oishi T, Nakata T. Synthesis 1990; 635
    • 1b Bode SE, Wolberg M, Müller M. Synthesis 2006; 557

      For reviews on aldol–Tishchenko reactions, see:
    • 2a Mahrwald R. Curr. Org. Chem. 2003; 7: 1713
    • 2b Mlynarski J. Eur. J. Org. Chem. 2006; 4779

      For reviews on cascade reactions, see:
    • 3a Nicolaou KC, Edmonds DJ, Bulger PG. Angew. Chem. Int. Ed. 2006; 45: 7134
    • 3b Grondal C, Jeanty M, Enders D. Nat. Chem. 2010; 2: 167

      For reviews on direct aldol reactions, see:
    • 4a Groger H, Vogl EM, Shibasaki M. Chem.–Eur. J. 1998; 4: 1137
    • 4b Trost BM, Brindle CS. Chem. Soc. Rev. 2010; 39: 1600
  • 5 Loog O, Mäeorg U. Tetrahedron: Asymmetry 1999; 10: 2411
  • 6 Mascarenhas CM, Miller SP, White PS, Morken JP. Angew. Chem. Int. Ed. 2001; 40: 601
    • 7a Gnanadesikan V, Horiuchi Y, Ohshima T, Shibasaki M. J. Am. Chem. Soc. 2004; 126: 7782
    • 7b Horiuchi Y, Gnanadesikan V, Ohshima T, Masu H, Katagiri K, Sei Y, Yamaguchi K, Shibasaki M. Chem.–Eur. J. 2005; 11: 5195
    • 8a Mlynarski J, Mitura M. Tetrahedron Lett. 2004; 45: 7549
    • 8b Mlynarski J, Jankowska J, Rakiel B. Chem. Commun. 2005; 4854
    • 8c Mlynarski J, Jankowska J, Rakiel B. Tetrahedron: Asymmetry 2005; 16: 1521
    • 8d Mlynarski J, Rakiel B, Stodulski M, Suszczynska A, Frelek J. Chem.–Eur. J. 2006; 12: 8158
    • 9a Rohr K, Herre R, Mahrwald R. Org. Lett. 2005; 7: 4499
    • 9b Rohr K, Herre R, Mahrwald R. J. Org. Chem. 2009; 74: 3744
    • 10a Nakajima M, Orito Y, Ishizuka T, Hashimoto S. Org. Lett. 2004; 6: 3763
    • 10b Orito Y, Hashimoto S, Ishizuka T, Nakajima M. Tetrahedron 2006; 62: 390
    • 10c Ichibakase T, Orito Y, Nakajima M. Tetrahedron Lett. 2008; 49: 4427
    • 10d Tanaka K, Ueda T, Ichibakase T, Nakajima M. Tetrahedron Lett. 2010; 51: 2168

      For recent examples of the use of dilithium binaphtholate as a catalyst, see:
    • 11a Schiffers R, Kagan HB. Synlett 1997; 1175
    • 11b Holmes IP, Kagan HB. Tetrahedron Lett. 2000; 41: 7453
    • 11c Hatano M, Ikeno T, Miyamoto T, Ishihara K. J. Am. Chem. Soc. 2005; 127: 10776
    • 11d Hatano M, Ikeno T, Matsumura T, Torii S, Ishihara K. Adv. Synth. Catal. 2008; 350: 1776
    • 11e Hatano M, Horibe T, Ishihara K. J. Am. Chem. Soc. 2010; 132: 56
  • 12 Ichibakase T, Nakajima M. Org. Lett. 2011; 13: 1579

    • For mechanistic studies of aldol–Tishchenko reactions, see:
    • 13a Evans DA, Hoveyda AH. J. Am. Chem. Soc. 1990; 112: 6447
    • 13b Burkhardt ER, Bergman RG, Heathcock CH. Organometallics 1990; 9: 30
    • 13c Mahrwald R, Costisella B. Synthesis 1996; 1087
    • 13d Bodnar PM, Shaw JT, Woerpel KA. J. Org. Chem. 1997; 62: 5674
    • 13e Abu-Hasanayn F, Streitwieser A. J. Org. Chem. 1998; 63: 2954
    • 13f Lu L, Chang H.-Y, Fang J.-M. J. Org. Chem. 1999; 64: 843
    • 13g Mascarenhas CM, Duffey MO, Liu S.-Y, Morken JP. Org. Lett. 1999; 1: 1427
    • 13h Markert M, Mahrwald R. Synthesis 2004; 1429
  • 14 Wu TR, Shen L, Chong JM. Org. Lett. 2004; 6: 2701
  • 15 Ishihara T, Yamaguchi K, Kuroboshi M, Utimoto K. Tetrahedron Lett. 1994; 35: 5263
  • 16 Acetti D, Brenna E, Fuganti C, Gatti FG, Serra S. Eur. J. Org. Chem. 2010; 142