(-)-(2S,3S)-2-ethyl-2-methyl-4-nitro-3-phenyl-butyraldehyde

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (-)-(2S,3S)-2-ethyl-2-methyl-4-nitro-3-phenyl-butyraldehyde
• 英文别名: (2S,3S)-2-ethyl-2-methyl-4-nitro-3-phenylbutyraldehyde；(2S,3S)-2-ethyl-2-methyl-4-nitro-3-phenylbutanal；2-ethyl-2-methyl-4-nitro-3-phenylbutyraldehyde
• 化学式: C₁₃H₁₇NO₃
• 分子量: 235.283
• InChiKey: NKFHZWSDBBZXAT-QWHCGFSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  反式硝基苯乙烯 、 2-甲基丁醛 在 4-二甲氨基吡啶 、 O-叔丁基-L-苏氨酸 、 磺酰胺 作用下， 以 甲苯 为溶剂， 反应 12.03h， 生成 (2R,3S)-2-ethyl-2-methyl-4-nitro-3-phenyl-butyraldehyde 、 (-)-(2S,3S)-2-ethyl-2-methyl-4-nitro-3-phenyl-butyraldehyde
  参考文献：
  名称：

  Practical access to highly enantioenriched quaternary carbon Michael adducts using simple organocatalysts

  摘要：

  一种由氨基酸（OtBu-L-苏氨酸）、氢键供体（硫酰胺）和胺碱（DMAP）组成的三组分催化剂体系可使α-支链醛加成到硝基烯烃，产率高且ee值优异。重要的是，该催化剂的负载量（5.0 摩尔%）和醛的化学计量（1.2-2.0 等量）均达到了报告中的最低水平，而且在大多数情况下都能观察到最佳的当前产物曲线。

  DOI：

  10.1039/c0ob00822b

文献信息

• Readily Accessible 9-epi-amino Cinchona Alkaloid Derivatives Promote Efficient, Highly Enantioselective Additions of Aldehydes and Ketones to Nitroolefins
  作者：Séamus H. McCooey、Stephen J. Connon

  DOI：10.1021/ol0628006

  日期：2007.2.1

  from commercially available starting materials, have been shown to promote highly enantio- and diastereoselective Michael-type addition reactions between enolizable carbonyl compounds and nitroalkenes of broad scope. The influence of both the absolute and relative stereochemistry at C-9 on catalyst performance has also been assessed. [reaction: see text].

  通过一锅法可从市售原料中获得的简单金鸡纳生物碱衍生物已显示出可促进可烯丙基的羰基化合物与广泛范围的硝基烯烃之间的高度对映和非对映选择性迈克尔型加成反应。还评估了C-9处绝对和相对立体化学对催化剂性能的影响。[反应：请参见文字]。
• Asymmetric Michael addition reactions of aldehydes with nitrostyrenes catalyzed by functionalized chiral ionic liquids
  作者：Qianying Zhang、Bukuo Ni、Allan D. Headley

  DOI：10.1016/j.tet.2008.03.073

  日期：2008.5

  A new class of pyrrolidine-based functionalized chiral ionic liquids (FCILs) has been developed and shown to be effective and reusable catalysts for the asymmetric Michael addition reactions. For the Michael addition reaction involving various aldehydes and nitrostyrenes, FCIL 6, in combination with trifluoroacetic acid as an additive, was found to be a very effective catalyst, compared to FCIL 3,

  已经开发出新型的基于吡咯烷的官能化手性离子液体（FCIL），并显示出它是用于不对称迈克尔加成反应的有效且可重复使用的催化剂。对于涉及各种醛和硝基苯乙烯的迈克尔加成反应，与结构略有变化的FCIL 3相比，发现FCIL 6与三氟乙酸结合作为添加剂是一种非常有效的催化剂。优异的收率（高达99％），良好的对映选择性（高达85％ee）和高非对映选择性（顺/反）对于这些反应，获得了高达97：3的比例）。FCIL催化剂易于回收和再利用至少五次，而不会显着丧失影响不对称反应结果的能力。
• Organocatalytic Direct Michael Reaction of Ketones and Aldehydes with β-Nitrostyrene in Brine
  作者：Nobuyuki Mase、Kaori Watanabe、Hidemi Yoda、Kunihiko Takabe、Fujie Tanaka、Carlos F. Barbas

  DOI：10.1021/ja060338e

  日期：2006.4.1

  We have developed a direct, asymmetric Michael reaction that can be performed in brine or seawater without addition of organic solvents. A bifunctional catalyst with long hydrophobic alkyl chains efficiently catalyzed Michael reactions and afforded the desired products in excellent yield with high enantiomeric excess, even when only an equal molar ratio of the donor to acceptor was used.
• Direct Asymmetric Organocatalytic Michael Reactions of α,α-Disubstituted Aldehydes with β-Nitrostyrenes for the Synthesis of Quaternary Carbon-Containing Products
  作者：Nobuyuki Mase、Rajeswari Thayumanavan、Fujie Tanaka、Carlos F. Barbas

  DOI：10.1021/ol049196o

  日期：2004.7.1

  Direct asymmetric catalytic Michael reactions have been performed using chiral-amine/acid bifunctional catalysts. Performed with 0.3 equiv of (S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine and 0.3 equiv of trifluoroacetic acid as the catalyst, the reaction of alpha,alpha-dialkylaldehydes with (E)-beta-nitrostyrene provided the alpha,alpha-dialkyl Michael products in up to 96% yield with up to 91% ee. With respect to enantioselectivity, L-proline was a poor catalyst of this class of Michael reactions.
• Solid Supported 9-Amino-9-deoxy-<i>epi</i>-quinine as Efficient Organocatalyst for Stereoselective Reactions in Batch and Under Continuous Flow Conditions
  作者：Riccardo Porta、Maurizio Benaglia、Francesca Coccia、Franco Cozzi、Alessandra Puglisi

  DOI：10.1002/adsc.201400821

  日期：2015.2.9

  AbstractPolystyrene‐supported 9‐amino‐9‐deoxy‐epi‐quinine was synthesized through co‐polymerization of an ad hoc‐designed chiral monomer with divinylbenzene, in the presence of azobis(isobutyronitile) (AIBN) as radical initiator and toluene and 1‐dodecanol as porogenic solvents. The heterogenized catalyst efficiently promoted the reaction of isobutyric aldehyde with β‐nitrostyrene, in very high yield and enantioselectivity, comparable or even higher than that of the homogeneous counterpart (up to 95% ee). The recyclability of the catalyst, its general applicability and its successful application to other reactions was also demonstrated. Finally, for the first time, a 9‐amino‐epi‐quinine derivative was employed to perform an enantioselective Michael reaction under continuous‐flow conditions; by using a home‐made, packed‐bed catalytic reactor, the aldehyde addition to nitrostyrene was successfully realized in flow mode, leading to the product in up to 93% ee.magnified image