Origins of stereoselectivity in intramolecular aldol reactions catalyzed by cinchona amines

被引：0
|
作者：
机构：
[1] Lam, Yu-Hong
[2] Houk, K.N.
来源：
Houk, K.N. (houk@chem.ucla.edu) | 1600年 / American Chemical Society卷 / 137期
关键词：
The intramolecular aldol condensation of 4-substituted heptane-2,6-diones leads to chiral cyclohexenones. The origins of the enantioselectivities of this reaction, disclosed by List et al. using a cinchona alkaloid-derived primary amine (cinchona amine) organocatalyst, have been determined with dispersion-corrected density functional theory (DFT). The stereocontrol hinges on the chair preference of the substrate-enamine intermediate and the conformational preferences of a hydrogen-bonded nine-membered aldol transition state containing eight heavy atoms. The conformations of the hydrogen-bonded ring in the various stereoisomeric transition structures have been analyzed in detail and shown to closely resemble the conformers of cyclooctane. A model of stereoselectivity is proposed for the cinchona amine catalysis of this reaction. The inclusion of Grimme's dispersion corrections in the DFT calculations (B3LYP-D3(BJ)) substantially improves the agreement of the computed energetics and experiment, attesting to the importance of dispersion effects in stereoselectivity. © 2015 American Chemical Society;
D O I：
暂无
中图分类号：
学科分类号：
摘要：
引用
收藏
相关论文
共 50 条
  • [1] Origins of Stereoselectivity in Intramolecular Aldol Reactions Catalyzed by Cinchona Amines
    Lam, Yu-hong
    Houk, K. N.
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (05) : 2116 - 2127
  • [2] Origins and predictions of stereoselectivity in intramolecular aldol reactions catalyzed by proline derivatives
    Cheong, PHY
    Houk, KN
    SYNTHESIS-STUTTGART, 2005, (09): : 1533 - 1537
  • [3] Origins of stereoselectivity in Cinchona alkaloid-primary amine-catalyzed intermolecular aldol reactions
    Yeh, Alexander J.
    Lam, Yu-hong
    Houk, Kendall N.
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2014, 248
  • [4] The origin of stereoselectivity in proline-catalyzed intramolecular aldol reactions
    Bahmanyar, S
    Houk, KN
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (51) : 12911 - 12912
  • [5] Origins of Stereoselectivity of Chiral Vicinal Diamine-Catalyzed Aldol Reactions
    Simon, Adam
    Yeh, Alexander J.
    Lam, Yu-hong
    Houk, K. N.
    JOURNAL OF ORGANIC CHEMISTRY, 2016, 81 (24): : 12408 - 12415
  • [6] Highly enantioselective direct aldol reaction catalyzed by cinchona derived primary amines
    Zheng, Bao-Lei
    Liu, Quan-Zhong
    Guo, Chuan-Sheng
    Wang, Xue-Lian
    He, Long
    ORGANIC & BIOMOLECULAR CHEMISTRY, 2007, 5 (18) : 2913 - 2915
  • [7] Stereoselectivity in (Acyloxy)borane-Catalyzed Mukaiyama Aldol Reactions
    Lee, Joshua M.
    Zhang, Xin
    Norrby, Per-Ola
    Helquist, Paul
    Wiest, Olaf
    JOURNAL OF ORGANIC CHEMISTRY, 2016, 81 (13): : 5314 - 5321
  • [8] Cinchona Alkaloid Catalyzed Asymmetric Desymmetrization of meso-Cyclic Anhydrides: The Origins of Stereoselectivity
    Dedeoglu, Burcu
    Catak, Saron
    Yildirim, Asli
    Bolm, Carsten
    Aviyente, Viktorya
    CHEMCATCHEM, 2015, 7 (24) : 4173 - 4179
  • [9] The origin of stereoselectivity in primary amino acid catalyzed intermolecular Aldol reactions
    Bassan, A
    Zou, WB
    Reyes, E
    Himo, F
    Córdova, A
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (43) : 7028 - 7032
  • [10] Origins of Stereoselectivity in Mannich Reactions Catalyzed by Chiral Vicinal Diamines
    Chen, Shuming
    Houk, K. N.
    JOURNAL OF ORGANIC CHEMISTRY, 2018, 83 (06): : 3171 - 3176
12345