(S)-2-((R)-1-(benzo[d][1,3]dioxol-6-yl)-2-nitroethyl)cyclohexanone | 84025-85-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: (S)-2-((R)-1-(benzo[d][1,3]dioxol-6-yl)-2-nitroethyl)cyclohexanone
• 英文别名: (S)-2-((R)-1-(benzo[d][1,3]dioxol-5-yl)-2-nitroethyl)-cyclohexanone；(S)-2-((R)-1-(benzo[d][1,3]dioxol-5-yl)-2-nitroethyl)cyclohexan-1-one；Cyclohexanone, 2-[(1R)-1-(1,3-benzodioxol-5-yl)-2-nitroethyl]-, (2S)-；(2S)-2-[(1R)-1-(1,3-benzodioxol-5-yl)-2-nitroethyl]cyclohexan-1-one
• CAS: 84025-85-4
• 化学式: C₁₅H₁₇NO₅
• 分子量: 291.304
• InChiKey: OJSFQMPLWDVTCD-RYUDHWBXSA-N

物化性质

• 熔点：
  144-145 °C
• 沸点：
  465.7±45.0 °C(Predicted)
• 密度：
  1.309±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  81.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  3,4-亚甲二氧-beta-硝基苯乙烯 、 环己酮 在 (S)-pyrrolidin-2-ylmethyl 2-methylpropane-2-sulfinate 作用下， 反应 24.0h， 以93%的产率得到(S)-2-((R)-1-(benzo[d][1,3]dioxol-6-yl)-2-nitroethyl)cyclohexanone
  参考文献：
  名称：

  脯氨醇亚磺酰基酯衍生物：在纯净条件下有机催化迈克尔将酮加成至硝基烯烃

  摘要：

  在室温下在无溶剂条件下以优异的收率实现了将酮高度地对映选择性和非对映选择性地将迈克尔加成到硝基烯烃上。 催化-不对称合成-酮-亚磺酸盐-迈克尔加成-硝基化合物

  DOI：

  10.1055/s-0029-1216637

文献信息

• Highly enantio- and diastereoselective Michael addition of cyclohexanone to nitroolefins catalyzed by a chiral glucose-based bifunctional secondary amine-thiourea catalyst
  作者：Aidang Lu、Peng Gao、Yang Wu、Youming Wang、Zhenghong Zhou、Chuchi Tang

  DOI：10.1039/b905306a

  日期：——

  A novel bifunctional thiourea bearing a saccharide-scaffold and a secondary amino group was synthesized, and was proven to be an effective organocatalyst for the asymmetric Michael reaction of cyclohexanone to both aryl and alkyl nitroolefins. The corresponding adducts were obtained with excellent diastereo- (up to >99/1 dr) and enantioselectivities (up to 97% ee).

  新颖的双功能 硫脲 带有糖-支架和仲氨基的化合物被合成，并被证明是一种有效的有机催化剂，用于不对称迈克尔反应 环己酮芳基和烷基硝基烯烃都可以。获得的非对映异构体（高达> 99/1 dr）和对映体选择性（高达97％ee）具有相应的加合物。
• An Ionic Liquid Containing L-Proline Moiety as Highly Efficient and Recyclable Chiral Organocatalyst for Michael Addition
  作者：Jiang Li、Xia Bing Li、Sha Sha Ma、Juan Liu、Ben Hao Li、Bao Lin Li

  DOI：10.1002/bkcs.10848

  日期：2016.8

  A novel chiral ionic liquid containing proline moiety was synthesized. It can be used as a highly efficient and recyclable chiral organocatalyst for Michael addition of cyclohexanone with (E)‐β‐nitroalkenes in methanol at room temperature. The Michael addition affords the corresponding products in satisfactory yields of isolated products (78–98%) with high diastereoselectivities and excellent enantioselectivities

  合成了一种新型的含有脯氨酸部分的手性离子液体。它可以用作高效和可回收的手性有机催化剂，用于在室温下在甲醇中将环己酮与（E）-β-硝基烯烃进行迈克尔加成反应。迈克尔加成物以高非对映选择性和出色的对映选择性（高达98％dr和高达99％ee）提供令人满意的分离产物（78-98％）的相应产物。催化剂可循环使用多达五次，而收率和立体选择性均不降低。
• Highly enantioselective Michael addition reactions in water catalyzed by an insoluble MPS-supported 4-sulfonamidyl prolinol tert-butyldiphenylsilyl ether
  作者：Yongming Chuan、Guihua Chen、Yungui Peng

  DOI：10.1016/j.tetlet.2009.04.011

  日期：2009.6

  The development of a highly efficient, insoluble, and non-swelling MPS-supported organocatalyst for the direct asymmetric Michael reaction of ketones and aldehydes to nitrostyrenes at room temperature in water is described. Excellent yields (up to 100%) and high stereoselectivities (up to 94% dr and 93% ee) were achieved with 10 mol % of the catalyst. The resin-bound catalyst was simply separated and

  描述了一种高效，不溶且不溶胀的MPS负载的有机催化剂的开发，该有机催化剂用于在室温下在水中将酮和醛直接进行不对称迈克尔反应，生成硝基苯乙烯。使用10摩尔％的催化剂可获得极佳的收率（最高100％）和高的立体选择性（最高94％dr和93％ee）。树脂结合的催化剂可以简单地通过过滤进行分离和回收，然后再用于六个连续的试验中，而活性和对映选择性均不会显着下降。
• Pyrrolidine based chiral organocatalyst for efficient asymmetric Michael addition of cyclic ketones to β-nitrostyrenes
  作者：Kamal Nain Singh、Paramjit Singh、Pushpinder Singh、Nand Lal、Sandeep Kumar Sharma

  DOI：10.1016/j.bmcl.2012.05.047

  日期：2012.7

  An efficient asymmetric Michael addition of cyclic ketones to β-nitrostyrenes using secondary diamine as an organocatalyst derived from l-proline and (R)-α-methylbenzyl amine has been described. This pyrrolidine based catalyst 1 was found to be very effective to synthesize various γ-nitrocarbonyl compounds in good yield (up to 81%) with excellent stereoselectivity (up to >99:1 dr and >99% ee).

  已经描述了使用仲二胺作为衍生自1-脯氨酸和（R）-α-甲基苄基胺的有机催化剂向β-硝基苯乙烯有效地将环状酮不对称迈克尔加成。发现该吡咯烷基催化剂1非常有效地以良好的产率（高达81：1 dr和> 99％ee）以良好的产率（高达81％）合成各种γ-硝基羰基化合物。
• Organocatalyzed asymmetric Michael addition by an efficient bifunctional carbohydrate–thiourea hybrid with mechanistic DFT analysis
  作者：Chandra S. Azad、Imran A. Khan、Anudeep K. Narula

  DOI：10.1039/c6ob02158a

  日期：——

  core scaffold were synthesized and examined as catalysts for the asymmetric Michael addition reaction of aryl/alkyl trans-β-nitrostyrenes over cyclohexanone and other Michael donors having active methylene. Excellent enantioselectivities (<95%), diastereoselectivities (<99%), and yields (<99%) were attained under solvent free conditions using 10 mol% of 1d0. The obtained results were explained through

  合成了一系列以D-葡萄糖为核心骨架的硫脲基双功能有机催化剂，并研究了其作为芳基/烷基反式-β-硝基苯乙烯在环己酮和其他具有活性亚甲基的迈克尔供体上的不对称迈克尔加成反应的催化剂。在无溶剂条件下，使用10 mol％的1d 0可获得极好的对映选择性（<95％），非对映选择性（<99％）和产率（<99％）。通过使用B3LYP / 6-311G（d，p）// B3LYP / 6-31G（d）基本集的DFT计算来解释获得的结果。QM / MM计算揭示了在速率确定步骤中环己酮作为溶剂和反应物的作用，赋予了31.91 kcal mol -1 能量形成产品。