3-[1'-hydroxy-1'-(3-nitrophenyl)methyl]tetrahydrothiopyran-4-one

• 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: 3-[1'-hydroxy-1'-(3-nitrophenyl)methyl]tetrahydrothiopyran-4-one
• 英文别名: 3-(1-hydroxy-1-(3-nitrophenyl)methyl)-tetrahydrothiopyran-4-one；(3R)-3-[(S)-hydroxy-(3-nitrophenyl)methyl]thian-4-one
• 化学式: C₁₂H₁₃NO₄S
• 分子量: 267.306
• InChiKey: ZNIOJZBJUGTUSL-CMPLNLGQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  108
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  四氢噻喃-4-酮 、 间硝基苯甲醛 在 C₂₇H₂₄N₂O₂ 作用下， 以 四氢呋喃 为溶剂， 反应 72.0h， 以43%的产率得到3-[1'-hydroxy-1'-(3-nitrophenyl)methyl]tetrahydrothiopyran-4-one
  参考文献：
  名称：

  Molecular-Sieves Controlled Diastereo- and Enantioselectivity: Unexpected Effect in the Organocatalyzed Direct Aldol Reaction

  摘要：

  一种高效的非对称有机催化剂被开发出来，用于酮和醛之间的直接aldol反应，以高立体选择性（anti/syn高达92:8，ee高达>99%）制备β-羟基酮。成功的关键在于使用了活化的分子筛（4 Å MS），其作为水的清除剂。还研究了水分或不同类型分子筛等添加剂对反应活性和立体选择性的影响。

  DOI：

  10.1055/s-2008-1072586

文献信息

• An efficient synthesis of chiral phosphinyl oxide pyrrolidines and their application to asymmetric direct aldol reactions
  作者：Xue-Wei Liu、Thanh Nguyen Le、Yunpeng Lu、Yongjun Xiao、Jimei Ma、Xingwei Li

  DOI：10.1039/b811581h

  日期：——

  Chiral pyrrolidine-based phosphinyl oxides were synthesized and their performance as organocatalysts for asymmetric direct aldol reactions was evaluated. High enantioselectivities and diastereoselectivies were achieved for a range of cyclic ketones and aromatic aldehydes.

  合成了手性吡咯烷基氧化膦，并评估了它们作为有机催化剂用于不对称直接羟醛反应的性能。对于一系列环酮和芳族醛，实现了高对映选择性和非对映选择性。
• A Highly Efficient Asymmetric Organocatalytic Aldol Reaction in a Ball Mill
  作者：Belén Rodríguez、Angelika Bruckmann、Carsten Bolm

  DOI：10.1002/chem.200700188

  日期：2007.6.4

  to >99 % enantiomeric excess (ee) have been obtained by proline catalysis in excellent yields under experimentally simple solvent-free conditions. Efficient mixing of all the components is accomplished by applying a mechanochemical technique (ball milling). The catalysis is air and moisture tolerant and can be performed with non-purified starting materials. Even mixtures of solely solid compounds react

  在实验简单的无溶剂条件下，通过脯氨酸催化以优异的收率获得了对映体过量（ee）高达99％以上的抗醛醇产品。通过使用机械化学技术（球磨）可以实现所有组分的有效混合。催化是耐空气和湿气的，并且可以用未纯化的起始原料进行。即使是纯固体化合物的混合物也会发生反应，通过部分均匀的（蜂蜜状）中间熔体产生（大部分为固体）产物。由于反应物比率几乎为1：1（避免普遍过量的酮），因此产物分离很容易导致高羟醛产物收率。
• Sterically and Electronically Tunable and Bifunctional Organocatalysts:  Design and Application in Asymmetric Aldol Reaction of Cyclic Ketones with Aldehydes
  作者：Jia-Rong Chen、Xin-Yong Li、Xiao-Ning Xing、Wen-Jing Xiao

  DOI：10.1021/jo0615089

  日期：2006.10.1

  tunable and bifunctional organocatalysts have been developed and evaluated in the direct aldol reaction of heterocyclic ketones. Catalysts with different substituents showed variable catalytic efficiency for analogous substrates, indicating the importance of fine-tuning the strength of the hydrogen bonding in the two NH groups. The reactions all proceeded in good to high yield and with excellent enantioselectivities

  在杂环酮的直接醛醇缩合反应中，已经开发并评估了可立体和电子可调的双功能有机催化剂。具有不同取代基的催化剂对类似的底物显示出不同的催化效率，表明微调两个NH基团中氢键强度的重要性。反应全部以良好至高收率进行，并且具有从90％至> 99％ee的优异对映选择性。在大多数情况下，抗羟醛加合物的非对映选择性高，为96/4至99/1。
• Ficin-catalyzed asymmetric aldol reactions of heterocyclic ketones with aldehydes
  作者：Jian-Ping Fu、Na Gao、Yang Yang、Zhi Guan、Yan-Hong He

  DOI：10.1016/j.molcatb.2013.06.016

  日期：2013.12

  Ficin from fig tree latex displayed a promiscuous activity to catalyze the direct asymmetric aldol reactions of heterocyclic ketones with aromatic aldehydes. Ficin showed good substrate adaptability to different heterocyclic ketones containing nitrogen, oxygen or sulfur. The enantioselectivities up to 81% ee and diastereoselectivities up to 86:14 (anti/syn) were achieved under the optimized reaction conditions. (C) 2013 Elsevier B.V. All rights reserved.
• Molecular-Sieves Controlled Diastereo- and Enantioselectivity: Unexpected Effect in the Organocatalyzed Direct Aldol Reaction
  作者：Jun-An Ma、Xiao-Juan Li、Guang-Wu Zhang、Lian Wang、Ming-Qing Hua

  DOI：10.1055/s-2008-1072586

  日期：2008.5

  An efficient asymmetric organocatalyst was developed for the direct aldol reaction between ketones and aldehydes to afford β-hydroxy ketones in high stereoselectivity (anti/syn up to 92:8, ee up to >99%). The key of the success was the use of activated molecular sieves (4 ŠMS), which acted as a water scavenger. The influence of additives such as water or different types of molecular sieves on the reactivity and stereoselectivity of the reaction was also studied.

  一种高效的非对称有机催化剂被开发出来，用于酮和醛之间的直接aldol反应，以高立体选择性（anti/syn高达92:8，ee高达>99%）制备β-羟基酮。成功的关键在于使用了活化的分子筛（4 Å MS），其作为水的清除剂。还研究了水分或不同类型分子筛等添加剂对反应活性和立体选择性的影响。