A Family of Chiral Ferrocenyl Diols: Modular Synthesis, Solid-State Characterization, and Application in Asymmetric Organocatalysis

被引:29
作者
Nottingham, Chris [1 ]
Muller-Bunz, Helge [1 ]
Guiry, Patrick J. [1 ]
机构
[1] Univ Coll Dublin, Ctr Synth & Chem Biol, Sch Chem, Dublin 4, Ireland
关键词
chirality; cycloaddition; diols; organocatalysis; planar chirality; C2-AND C1-SYMMETRIC NITROGEN; DIELS-ALDER REACTIONS; SULFUR DERIVATIVES; ENANTIOSELECTIVE SYNTHESIS; KINETIC RESOLUTION; CATALYSIS; LIGANDS; ANALOGS; PHOSPHORUS; TADDOL;
D O I
10.1002/anie.201604840
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Readily available chiral diol scaffolds are useful as sources of chirality for asymmetric synthesis, however, few such scaffolds are readily available in enantiopure form. Reported herein is a cheap and modular synthesis of a novel family of chiral ferrocenyl diols in excellent yields with excellent enantio- and diastereoselectivity (>99% ee and 99% de). These diols possess not only planar and central chirality, but also axial chirality around the central iron atom. Characterization of these diols by X-ray crystallography revealed intra- and intermolecular hydrogen-bond networks depending on substitution at the carbinol positions. The potential of these diols as catalysts was subsequently demonstrated in an asymmetric hetero-Diels-Alder reaction which provided cycloadducts in up to 84% yield with eevalues ranging from -92 to +72%.
引用
收藏
页码:11115 / 11119
页数:5
相关论文
共 45 条
  • [1] The synthesis of N,O-ferrocenyl pyrrolidine-containing ligands and their application in the diethyl- and diphenylzinc addition to aromatic aldehydes
    Ahern, Theresa
    Muller-Bunz, Helge
    Guiry, Patrick J.
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (20) : 7596 - 7602
  • [2] Origin of enantioselection in hetero-Diels-Alder reactions catalyzed by naphthyl-TADDOL
    Anderson, Christopher D.
    Dudding, Travis
    Gordillo, Ruth
    Houk, K. N.
    [J]. ORGANIC LETTERS, 2008, 10 (13) : 2749 - 2752
  • [3] [Anonymous], 2006, Angew. Chem
  • [4] [Anonymous], 2007, ANGEW CHEM
  • [5] [Anonymous], 2013, ANGEW CHEM, V125, P522
  • [6] Recent applications of chiral ferrocene ligands in asymmetric catalysis
    Arrayas, Ramon Gomez
    Adrio, Javier
    Carretero, Juan Carlos
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (46) : 7674 - 7715
  • [7] Syntheses and applications of C2-symmetric chiral diols
    Bhowmick, Kartick C.
    Joshi, Navalkishore N.
    [J]. TETRAHEDRON-ASYMMETRY, 2006, 17 (13) : 1901 - 1929
  • [8] From a chiral switch to a ligand portfolio for asymmetric catalysis
    Blaser, Hans-Ulrich
    Pugin, Benoit
    Spindler, Felix
    Thommen, Marc
    [J]. ACCOUNTS OF CHEMICAL RESEARCH, 2007, 40 (12) : 1240 - 1250
  • [9] Boshra R., 2008, ANGEW CHEM, V120, P1150
  • [10] Allylation of ketones with a ferrocene-based planar chiral lewis acid
    Boshra, Ramez
    Doshi, Ami
    Jaekle, Frieder
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (06) : 1134 - 1137