Base-Catalyzed Direct Aldolization of α-Alkyl-α-Hydroxy Trialkyl Phosphonoacetates

Authors

  • Michael T. Corbett,

    1. Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599 (USA)
    Search for more papers by this author
  • Dr. Daisuke Uraguchi,

    1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho B2-3(611), Chikusa, Nagoya 464-8603 (Japan)
    Search for more papers by this author
  • Prof. Dr. Takashi Ooi,

    Corresponding author
    1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho B2-3(611), Chikusa, Nagoya 464-8603 (Japan)
    • Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho B2-3(611), Chikusa, Nagoya 464-8603 (Japan)
    Search for more papers by this author
  • Prof. Dr. Jeffrey S. Johnson

    Corresponding author
    1. Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599 (USA)
    • Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599 (USA)
    Search for more papers by this author

  • The project described was supported by the National Institute of General Medical Sciences (Award R01 GM084927), the NEXT program, and a Grant-in-Aid for Scientific Research on Innovative Areas “Advanced Molecular Transformations by Organocatalysts” from MEXT. M.T.C. acknowledges a JSPS/NSF EAPSI Fellowship and the Global COE program in Chemistry of Nagoya University. Additional support from Novartis is gratefully acknowledged. X-ray crystallographic analysis was performed by Yusuke Ueki of Nagoya University.

Abstract

original image

Phosphor auf Wanderschaft: Die katalytische direkte Aldoladdition von α-Hydroxytrialkylphosphonacetaten an Aldehyde liefert α-Hydroxy-β-phosphonyloxyester (siehe Schema). Das vollständig substituierte Glycolatenolat-Intermediat wird in situ unter milden Bedingungen durch eine [1,2]-Phosphonat-Phosphat-Umlagerung erzeugt. Chirale Iminophosphoran-Katalysatoren sorgen für hohe Enantio- und Diastereoselektivitäten.

Ancillary