(-)-2-[2,2-bis(phenylsulfonyl)ethyl]-3,3-dimethylbutanal

• 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: (-)-2-[2,2-bis(phenylsulfonyl)ethyl]-3,3-dimethylbutanal
• 英文别名: (2R)-2-[2,2-bis(benzenesulfonyl)ethyl]-3,3-dimethylbutanal
• 化学式: C₂₀H₂₄O₅S₂
• 分子量: 408.54
• InChiKey: SHRSFLAQYNQDQK-INIZCTEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  3,3-二甲基丁醛 、 1,1-双(苯基磺酰基)乙烯 在 (2S)-2-[二苯基[(三甲基硅酯)氧基]甲基]-吡咯烷 作用下， 以 氯仿 为溶剂， 反应 2.0h， 生成 (+)-2-[2,2-bis(phenylsulfonyl)ethyl]-3,3-dimethylbutanal 、 (-)-2-[2,2-bis(phenylsulfonyl)ethyl]-3,3-dimethylbutanal
  参考文献：
  名称：

  对映选择性有机催化共轭加成醛到乙烯基砜和乙烯基膦酸酯作为具有挑战性的迈克尔受体。

  摘要：

  手性骨架：具有吡咯烷骨架的手性胺可高产率地催化多种醛的对映选择性共轭加成反应，生成各种乙烯基砜和膦酸乙烯酯，对映选择性高达> 99％ee（参见方案）。迈克尔加合物的高通用性可以通过各种官能化以及光学纯度的保留来举例说明。

  DOI：

  10.1002/chem.200801892

文献信息

• First Organocatalyzed Asymmetric Michael Addition of Aldehydes to Vinyl Sulfones
  作者：Sarah Mossé、Alexandre Alexakis

  DOI：10.1021/ol051488h

  日期：2005.9.1

  [reaction: see text] The first asymmetric direct Michael addition of aldehydes to vinyl sulfones catalyzed by N-iPr-2,2'-bipyrrolidine is described. 1,4-Adducts are obtained in good yields and enantioselectivities. The determination of absolute configuration allowed us to postulate a Si,Si transition state model, as shown previously for nitroolefins.

  [反应：见正文]描述了由N-iPr-2,2'-联吡咯烷催化的醛向乙烯基砜的第一次不对称直接迈克尔加成。以良好的产率和对映选择性获得1，4-加合物。绝对构型的确定使我们能够假设一个Si，Si过渡态模型，如先前对硝基烯烃所示。
• Enantioselective Organocatalytic Conjugate Addition of Aldehydes to Vinyl Sulfones and Vinyl Phosphonates as Challenging Michael Acceptors
  作者：Sarah Sulzer-Mossé、Alexandre Alexakis、Jiri Mareda、Guillaume Bollot、Gerald Bernardinelli、Yaroslav Filinchuk

  DOI：10.1002/chem.200801892

  日期：2009.3.16

  Chiral framework: Chiral amines with pyrrolidine frameworks catalyze the enantioselective conjugate addition of a wide range of aldehydes to various vinyl sulfones and vinyl phosphonates in high yields and with enantioselectivities up to >99 % ee (see scheme). The high versatility of the Michael adducts is exemplified by various functionalizations with conservation of the optical purity.

  手性骨架：具有吡咯烷骨架的手性胺可高产率地催化多种醛的对映选择性共轭加成反应，生成各种乙烯基砜和膦酸乙烯酯，对映选择性高达> 99％ee（参见方案）。迈克尔加合物的高通用性可以通过各种官能化以及光学纯度的保留来举例说明。
• 1,2-Sulfone rearrangement in organocatalytic reactions
  作者：Adrien Quintard、Alexandre Alexakis

  DOI：10.1039/c0ob00818d

  日期：——

  The 1,2-sulfone rearrangement resulting from nucleophilic addition to bis activated vinyl-sulfones has been studied in more detail. Various nucleophiles activated by different types of catalysts (enamine, Brönsted base, thiourea) are able to promote such rearrangement in excellent yields and moderate to excellent enantioselectivities (up to 94% ee). Mechanistic studies have led to a better understanding of the mechanism and allowed its application to other electrophiles such as vinyl-sulfone acrylates.

  对双活化的乙烯基亚磺酸酯进行亲核加成所导致的1,2-亚磺酸重排已被更深入地研究。不同类型催化剂（如烯胺、布朗斯特碱、硫脲）激活的各种亲核试剂能够以极好的产率和中到优良的对映选择性（最高达94% ee）促进这种重排。机理研究使我们对该机制有了更好的理解，并使其能够应用于其他电亲核试剂，如乙烯基亚磺酸丙烯酸酯。
• Diversity-Oriented Synthesis towards Conceptually New Highly Modular Aminal-Pyrrolidine Organocatalysts
  作者：Adrien Quintard、Chloée Bournaud、Alexandre Alexakis

  DOI：10.1002/chem.200801212

  日期：2008.8.28
• Conformationally Stabilized Catalysts by Fluorine Insertion: Tool for Enantioselectivity Improvement
  作者：Adrien Quintard、Jean-Baptiste Langlois、Daniel Emery、Jiri Mareda、Laure Guénée、Alexandre Alexakis

  DOI：10.1002/chem.201102757

  日期：2011.11.25

  F rigid cats: The power of conformationally stabilized catalysts is demonstrated. By taking appropriate advantage of fluorine insertion (see scheme), purely conformational catalyst design led to a notable improvement in enantioselectivities from around 70 % to 91–98.5 % ee. The other advantage of this approach is the better understanding of the origin of the stereoselectivity in the given catalytic

  F刚性猫：证明了构象稳定的催化剂的功能。通过充分利用氟的插入（参见方案），纯构象催化剂的设计可将对映选择性从大约70％ee显着提高到91–98.5％ee。这种方法的另一个优点是可以更好地理解给定催化体系中立体选择性的起源。