Asymmetric 1,4-Addition of Oxazolones to Nitroalkenes by Bifunctional Cinchona Alkaloid Thiourea Organocatalysts: Synthesis of α,α-Disubstituted α-Amino Acids

被引:101
作者
Aleman, Jose [1 ]
Milelli, Andrea [1 ]
Cabrera, Silvia [1 ]
Reyes, Efraim [1 ]
Jorgensen, Karl Anker [1 ]
机构
[1] Aarhus Univ, Dept Chem, Danish Natl Res Fdn Ctr Catalysis, DK-8000 Aarhus C, Denmark
基金
新加坡国家研究基金会;
关键词
amino acids; organo-catalysis; oxazolones; thiourea;
D O I
10.1002/chem.200802030
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
An easy and simple synthetic approach to optically active a,a-quaternary a-amino acids using asymmetric organocatalysis is presented. The addition of oxazolones to nitroalkenes catalyzed by thiourea cinchona derivatives provides the corresponding a,a-quaternary a-amino acid derivatives with good yields, excellent diastereoselectivities (up to 98% dr), and from moderate to good enantioselectivities (up to 92% ee). The reaction can be performed on a large scale. The optically active oxazolone-nitroalkene addition products can be opened in a one-pot reaction to the corresponding ester-amide derivatives. Additional transformations are also presented, such as the synthesis of amino esters, amino acids, and transformation into 3,4-disubstituted pyrrolidin-2-ones.
引用
收藏
页码:10958 / 10966
页数:9
相关论文
共 114 条
  • [1] New strategies for organic catalysis: The first highly enantioselective organocatalytic Diels-Alder reaction
    Ahrendt, KA
    Borths, CJ
    MacMillan, DWC
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (17) : 4243 - 4244
  • [2] Organocatalytic asymmetric conjugate additions
    Almasi, Diana
    Alonso, Diego A.
    Najera, Carmen
    [J]. TETRAHEDRON-ASYMMETRY, 2007, 18 (03) : 299 - 365
  • [3] Novel bifunctional chiral urea and thiourea derivatives as organocatalysts:: Enantioselective nitro-Michael reaction of malonates and diketones
    Andres, Jose M.
    Manzano, Ruben
    Pedrosa, Rafael
    [J]. CHEMISTRY-A EUROPEAN JOURNAL, 2008, 14 (17) : 5116 - 5119
  • [4] [Anonymous], 2008, ANGEW CHEM, DOI DOI 10.1002/ANGE.200705523
  • [5] [Anonymous], 2006, ANGEW CHEM, V118, P1550
  • [6] [Anonymous], 2007, Chem. Rev
  • [7] Second-generation organocatalysts for the highly enantioselective dynamic kinetic resolution of azlactones
    Berkessel, A
    Mukherjee, S
    Cleemann, F
    Müller, TN
    Lex, J
    [J]. CHEMICAL COMMUNICATIONS, 2005, (14) : 1898 - 1900
  • [8] Berkessel A, 2005, ASYMMETRIC ORGANOCATALYSIS: FROM BIOMIMETIC CONCEPTS TO APPLICATIONS IN ASYMMETRIC SYNTHESIS, P1, DOI 10.1002/3527604677
  • [9] Berner OM, 2002, EUR J ORG CHEM, V2002, P1877
  • [10] Asymmetric organocatalytic β-hydroxylation of α,β-unsaturated aldehydes
    Bertelsen, Soren
    Diner, Peter
    Johansen, Rasmus Lyng
    Jorgensen, Karl Anker
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (06) : 1536 - +