tert-butyl (1R,2R,3R,4S,5R,6S)-2-benzyl-1-hydroxy-4,6-dinitro-3,5-diphenylcyclohexanecarboxylate | 1218815-53-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: tert-butyl (1R,2R,3R,4S,5R,6S)-2-benzyl-1-hydroxy-4,6-dinitro-3,5-diphenylcyclohexanecarboxylate
• 英文别名: (1R,2R,3R,4S,5R,6S)-tert-butyl 2-benzyl-1-hydroxy-4,6-dinitro-3,5-diphenylcyclohexanecarboxylate；tert-butyl (1R,2R,3R,4S,5R,6S)-2-benzyl-1-hydroxy-4,6-dinitro-3,5-diphenylcyclohexane-1-carboxylate
• CAS: 1218815-53-2
• 化学式: C₃₀H₃₂N₂O₇
• 分子量: 532.593
• InChiKey: XJWPJHUDFPJRNG-PJOJMHBUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  39
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  138
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  β-硝基苯乙烯 、 tert-butyl 2-oxo-4-phenylbutanoate 在 C₄₂H₅₇N₅O₃S 作用下， 以 四氢呋喃 为溶剂， 反应 72.5h， 以93%的产率得到tert-butyl (1R,2R,3R,4S,5R,6S)-2-benzyl-1-hydroxy-4,6-dinitro-3,5-diphenylcyclohexanecarboxylate
  参考文献：
  名称：

  不对称有机催化迈克尔/迈克尔/亨利序列构建具有六个邻位立体中心的环己烷

  摘要：

  已经建立了一种有效的、不对称的、催化的、α-酮酯和硝基烯烃之间的三重级联反应，以高产率和高对映选择性构建具有六个邻位立体中心的环己烷。双功能胍-酰胺有机催化剂通过布朗斯台德碱和氢键协同催化被证明可用于迈克尔/迈克尔/亨利序列。

  DOI：

  10.1055/s-0036-1588940

文献信息

• A Highly Diastereo- and Enantioselective Reaction for Constructing Functionalized Cyclohexanes: Six Contiguous Stereocenters in One Step
  作者：Dengjian Shi、Yinjun Xie、Han Zhou、Chungu Xia、Hanmin Huang

  DOI：10.1002/anie.201107495

  日期：2012.1.27

  Just mix to get six: Six contiguous stereocenters, including one quaternary stereocenter, and three CC bonds are created by a new copper‐catalyzed tandem reaction (see scheme). Rigid chiral diamine ligands enabled this asymmetric tandem reaction to proceed with excellent stereoselectivity (complete diastereoselectivity and high enantioselectivity) and high yield under mild reaction conditions.

  只需混合即可得到六个：六价连续的立体中心（包括一个四级立体中心）和三个CC键是通过新的铜催化串联反应生成的（请参见方案）。刚性手性二胺配体使这种不对称串联反应能够在温和的反应条件下以优异的立体选择性（完全的非对映选择性和高对映选择性）和高收率进行。
• Diastereo- and Enantioselective Conjugate Addition of α-Ketoesters to Nitroalkenes Catalyzed by a Chiral Ni(OAc)₂ Complex under Mild Conditions
  作者：Ayako Nakamura、Sylvain Lectard、Daisuke Hashizume、Yoshitaka Hamashima、Mikiko Sodeoka

  DOI：10.1021/ja909457b

  日期：2010.3.31

  A highly efficient, catalytic, diastereo- and enantioselective conjugate addition of alpha-ketoesters to nitroalkenes has been devised. The reaction was applicable to various substrates. Notably, the combination of endogenous and exogenous bases was effective, allowing a small amount of the catalyst (0.1-1 mol % Ni) to promote the reaction efficiently. The synthetic utility of this reaction was demonstrated

  α-酮酯与硝基烯烃的高效、催化、非对映选择性和对映选择性共轭加成已被设计出来。该反应适用于各种底物。值得注意的是，内源性和外源性碱的组合是有效的，允许少量的催化剂（0.1-1 mol % Ni）有效地促进反应。该反应的合成效用在取代的吡咯烷衍生物的合成中得到证明，其立体化学与生物学上重要的天然产物如红藻氨酸密切相关。
• Asymmetric conjugate addition of α-keto esters to nitroolefins catalyzed by chiral CuII hydroxo complexes
  作者：Ayako Nakamura、Sylvain Lectard、Ryo Shimizu、Yoshitaka Hamashima、Mikiko Sodeoka

  DOI：10.1016/j.tetasy.2010.04.009

  日期：2010.7

  As a part of our research project on hard anion-late transition metal complexes as mild acid-base catalysts, we describe herein that Cu-II hydroxo complexes having chiral N-substituted-diaminocyclohexanes are mild and selective catalysts, which are applicable to the catalytic asymmetric conjugate addition of alpha-keto esters to nitroolefins. The reaction proceeded diastereoselectively without the detectable formation of self-aldol products, affording the corresponding coupling products with anti-stereochemistry in an enantioselective manner. (C) 2010 Elsevier Ltd. All rights reserved.