(R)-3-[hydroxy-(3-nitrophenyl)methyl]but-3-en-2-one | 917615-16-8

• 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: (R)-3-[hydroxy-(3-nitrophenyl)methyl]but-3-en-2-one
• 英文别名: (R)-3-[hydroxy(3-nitrophenyl)methyl]but-3-en-2-one；3-[(R)-hydroxy-(3-nitrophenyl)methyl]but-3-en-2-one
• CAS: 917615-16-8
• 化学式: C₁₁H₁₁NO₄
• 分子量: 221.213
• InChiKey: WLZNSKOTSBIWOJ-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  83.1
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  间硝基苯甲醛 、 丁烯酮 在 1-[(1R,2R)-2-diphenylphosphanylcyclohexyl]-3-phenylthiourea 作用下， 以 氯仿 为溶剂， 反应 0.5h， 以71%的产率得到(R)-3-[hydroxy-(3-nitrophenyl)methyl]but-3-en-2-one
  参考文献：
  名称：

  芳香醛与甲基乙烯基酮的对映选择性森田-贝利斯-希尔曼反应中的手性膦硫脲有机催化剂

  摘要：

  新型的手性膦硫脲已被开发为有效的有机催化剂，用于芳香醛与甲基乙烯基酮的对映选择性Morita-Baylis-Hillman反应。反应在非常温和的条件下进行，可以在短时间内以高达94％ee的良好收率获得所需的产物。

  DOI：

  10.1016/j.tetlet.2008.08.042

文献信息

• Chiral Tertiary Amine/L-Proline Cocatalyzed Enantioselective Morita–Baylis–Hillman (MBH) Reaction
  作者：Hongying Tang、Guofeng Zhao、Zhenghong Zhou、Peng Gao、Liangnian He、Chuchi Tang

  DOI：10.1002/ejoc.200700794

  日期：2008.1

  cocatalytic reactions with the two enantiomers of chiral amine 4 and L-proline revealed that it is the proline stereochemistry that determines the configuration of the newly formed chiral center. In addition, the existence of the free hydroxy group in amine 4a enhanced the enantioselectivity of the reaction. Based on these findings, a plausible mechanism for this cocatalytic MBH reaction has been proposed

  从容易获得的手性来源开始，已经合成了四种类型的手性胺。已发现这些手性胺与 L-脯氨酸结合是甲基乙烯基酮 (MVK) 和芳香醛之间不对称 Morita-Baylis-Hillman (MBH) 反应的有效助催化剂。相应的加合物以合理的化学产率和良好的对映选择性（高达 83% ee）形成。此外，与手性胺 4 和 L-脯氨酸的两种对映异构体的平行共催化反应表明，脯氨酸立体化学决定了新形成的手性中心的构型。此外，胺4a中游离羟基的存在提高了反应的对映选择性。基于这些发现，已经提出了这种助催化 MBH 反应的合理机制。
• Brucine N-oxide-catalyzed Morita–Baylis–Hillman reaction of vinyl ketones: a mechanistic implication of dual catalyst system with proline
  作者：Kyungsoo Oh、Jian-Yuan Li、Jinhyang Ryu

  DOI：10.1039/c003667f

  日期：——

  The brucine N-oxide promoted Morita–Baylis–Hillman (MBH) reaction of vinyl ketones with aldehydes has been achieved. The corresponding asymmetric version of MBH reaction was also investigated, and the electron-deficient aryl aldehydes have emerged as suitable reaction partners for vinyl ketones; where proline was employed as a co-catalyst. In this dual catalyst system, proline is believed to form iminium

  原始的N氧化物促进了Morita–Baylis–Hillman（MBH）已经实现了乙烯基酮与醛的反应。对应的不对称版本MBH还对反应进行了研究，并且出现了缺电子的芳基醛作为乙烯基酮的合适反应伙伴。在哪里脯氨酸被用作助催化剂。在这种双重催化剂系统中，脯氨酸认为N-氧化物与缺电子的芳基醛形成亚胺中间体，而N-氧化物活化乙烯基酮以通过共轭加成提供烯醇化物。结合这两种中间体后，通过控制速率确定步骤可以得到高对映选择性的MBH产物。H桥接的椅子状过渡状态。本质上，结果MBH发现产物醇类干扰中间体，烯醇化物和脯氨酸亚胺鎓中间体两者的形成，因此观察到的产物的对映选择性在进一步反应转化时减弱，可能是由于自催化作用。本研究为衍生自缺电子的芳基醛和脯氨酸。
• Methods for the synthesis of chiral sulfur heterocycles and their application in the asymmetric Baylis–Hillman reactions
  作者：Mariappan Periasamy、Ramani Gurubrahamam、Gopal P. Muthukumaragopal

  DOI：10.1016/j.tetasy.2013.03.021

  日期：2013.5

  Enantiomerically pure (2S,6S)-2,6-diphenyltetrahydro-2H-thiopyran, (2S)-2-phenyltetrahydro thiophene, and (2S)-2-phenyltetrahydro-2H-thiopyran were prepared in 70-72% yields and with 86-99% ee via cyclization of the corresponding dimesylate in an S(N)2 cyclization reaction using sodium sulfide nonahydrate. The results on the application of various chiral sulfides in asymmetric Baylis-Hillman reactions are also described. (C) 2013 Elsevier Ltd. All rights reserved.
• 10.24820/ark.5550190.p011.072dummy2
  作者：Aydin, A. Ebru

  DOI：10.24820/ark.5550190.p011.072dummy2

  日期：——
• A New BINOL-Derived Chiral Bifunctional Phosphine Organocatalyst: Preparation and Application in Asymmetric (Aza)-Morita-Baylis-Hillman Reactions
  作者：Chunzhang Wang、Lijun Wang、San Zeng、Silong Xu、Zhengjie He

  DOI：10.1080/10426507.2012.761987

  日期：2013.11.1

  A new BINOL-derived chiral bifunctional phosphine has been designed and successfully prepared, which features a cyclic substructure of 1,3,5-diazaphosphinane. This chiral phosphine possesses good air stability in solid state, and it can be conveniently used as a relatively more nucleophilic phosphine organocatalyst. Preliminary investigations showed that it could generally afford fair to excellent yields but only modest enantioselectivity in the (aza)-Morita-Baylis-Hillman reactions of activated olefins such as ethyl acrylate and methyl vinyl ketone with aldehydes or imines. [Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus Sulfer and Silicon and the Related Elements for the following free supplemental files: Additional text and figures.]