N-cyclohexyl-2,2-dimethyl-1,3-dioxan-5-imine | 371153-91-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N-cyclohexyl-2,2-dimethyl-1,3-dioxan-5-imine
• CAS: 371153-91-2
• 化学式: C₁₂H₂₁NO₂
• 分子量: 211.304
• InChiKey: LDVQLMDBWWOORH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  30.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-cyclohexyl-2,2-dimethyl-1,3-dioxan-5-imine 在 正丁基锂 、 sodium hexamethyldisilazane 、 二乙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 6.0h， 生成 4-(hepta-4,6-dienyl)-5-(tertbutyldimethylsilyloxy)-2,2-dimethyl-4H-[1.3]dioxin
  参考文献：
  名称：

  Stereoselective Preparation of (Z)-2-(Trialkylsilyloxy)-2-alkenals by Retrocycloaddition Reactions of 4H-4-Alkyl-5-(trialkylsilyloxy)-1,3-dioxins. Useful Reactants for Lewis Acid Catalyzed [4 + 3] Cyclizations

  摘要：

  [GRAPHICS]Retrocycloadditions of 4H-4-alkyl-5-(trialylsilyloxy)-1,3-dioxins proceed smoothly in refluxing toluene to afford (Z)-2-(trialkylsilyloxy)-2-alkenals with complete stereos electivity. These enals undergo Sasaki-type [4 + 3] cyclizations with dienes in the presence of Lewis acids, in many instances with excellent regio- and/or stereoselectivity.

  DOI：

  10.1021/ol016668f
• 作为产物：
  描述：

  2,2-二甲基-1,3-二恶烷-5-酮 、 环己胺 以 甲苯 为溶剂， 反应 14.0h， 生成 N-cyclohexyl-2,2-dimethyl-1,3-dioxan-5-imine
  参考文献：
  名称：

  对映选择性脱羧烷基化反应：催化剂开发、底物范围和机理研究

  摘要：

  在钯配合物与各种膦恶唑啉 (PHOX) 配体的存在下，通过不稳定的前手性烯醇化亲核试剂对烯丙基和炔丙基亲电子试剂进行新颖的对映选择性烷基化来获得 α-季酮。三类烯醇化物前体获得了优异的产率和高对映体过量：烯醇碳酸酯、烯醇硅烷和外消旋 β-酮酯。这些底物类别中的每一种在产率和对映选择性方面都具有几乎相同的效率。报道了催化剂的发现和开发、反应条件的优化、反应范围的探索以及在靶向合成中的应用。实验观察表明，这些烷基化反应通过一种不寻常的内球机制发生，涉及前手性烯醇化亲核试剂直接与钯中心结合。

  DOI：

  10.1002/chem.201003383

文献信息

• Formal synthesis of englerin A utilizing regio- and diastereoselective [4+3] cycloaddition
  作者：Shuichi Hagihara、Kengo Hanaya、Takeshi Sugai、Mitsuru Shoji

  DOI：10.1038/ja.2017.91

  日期：2018.2

  inhibitory activities against renal cancer cell lines. We synthesized the key tricyclic intermediate from commercially available 2,2-dimethyl-1,3-dioxan-5-one via regio- and diastereoselective [4+3] cycloaddition between the formyl enol silyl ether and the disubstituted furan, in 4.8% total yield over 10 steps.

  Englerin A，一种从卷柏（Phyllanthus engleri）分离出的愈创树倍半萜烯，对肾癌细胞具有高度有效的选择性生长抑制活性。我们通过甲酰基烯醇甲硅烷基醚与二取代呋喃之间的区域和非对映选择性[4 + 3]环加成反应，由市售的2,2-二甲基-1,3-二恶烷-5-酮合成了关键的三环中间体，总计4.8％产量超过10个步骤。
• Synthesis of (<i>Z</i>)-2-Acyl-2-enals via Retrocycloadditions of 5-Acyl-4-alkyl-4<i>H</i>-1,3-dioxins:  Application in the Total Synthesis of the Cytotoxin (±)-Euplotin A
  作者：Ronald A. Aungst、Raymond L. Funk

  DOI：10.1021/ja011470b

  日期：2001.9.1
• Catalytic Enantioselective Alkylation of Substituted Dioxanone Enol Ethers: Ready Access to C(α)-Tetrasubstituted Hydroxyketones, Acids, and Esters
  作者：Masaki Seto、Jennifer L. Roizen、Brian M. Stoltz

  DOI：10.1002/anie.200801424

  日期：2008.8.25

  The catalytic enantioselective formation of tetrasubstituted α-alkoxycarbonyl compounds is an ongoing challenge to synthetic chemists.[1] Fully-substituted α-hydroxyesters and acids comprise essential components of, and building blocks for, many bioactive natural products. These include quinic acid (1), cytotoxic leiodolide A (2),[2] and the anti-cancer agents in the harringtonine series (3a–f), whose activities depend dramatically on the presence and composition of an α-hydroxyester side-chain.[3] While many approaches to these important moieties exist,[4,5] we envisioned applying our recently developed palladium-catalyzed methods for the formation of enantioenriched all-carbon quaternary stereocenters in cyclic alkanones[6] to a general synthesis of C(α)-tetrasubstituted hydroxy carbonyl compounds.[7]
• A Facile Construction of Bi- or Tricyclic Skeletons by Nickel-Catalyzed Stereoselective Cyclization of Alkynylcycloalkanone
  作者：Nozomi Saito、Yasuyuki Sugimura、Yoshihiro Sato

  DOI：10.1021/ol101329d

  日期：2010.8.6

  A nickel-catalyzed intramolecular cyclization of alkynylalkanone in the presence of Et(3)SiH using an NHC ligand produced various carbo- and heterocycles In a stereoselective manner. The reaction would proceed via formation of oxanickelacycle followed by sigma-bond metathesis with silane to give a bi- or tricyclic compound.