methyl 1,6-dihydroxy-cyclohex-2-encarboxylate | 1210906-76-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 1,6-dihydroxy-cyclohex-2-encarboxylate
• 英文别名: methyl (1S,6R)-1,6-dihydroxycyclohex-2-enecarboxylate；methyl (1S,6R)-1,6-dihydroxycyclohex-2-ene-1-carboxylate
• CAS: 1210906-76-5
• 化学式: C₈H₁₂O₄
• 分子量: 172.181
• InChiKey: SEHYYTXDMBGUBX-SVRRBLITSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 1,6-dihydroxy-cyclohex-2-encarboxylate 在 2-碘酰基苯甲酸 作用下， 以 二甲基亚砜 为溶剂， 反应 15.5h， 以59%的产率得到(-)-methyl (S)-1-hydroxy-6-oxo-cyclohex-2-encarboxylate
  参考文献：
  名称：

  Chemoenzymatic Synthesis of Idesolide from Benzoic Acid

  摘要：

  Idesolide是通过五个步骤从苯甲酸合成的，过程中首先通过碱催化的双聚反应将二醇转化为羟基酮酯，而该二醇是通过R. eutrophus B9对苯甲酸进行全细胞发酵得到的。

  DOI：

  10.1055/s-0030-1259694
• 作为产物：
  描述：

  methyl (1R,6S)-6-(tert-butyldimethylsilyloxy)-1-hydroxy-2-cyclohexene-1-carboxylic acid 在 氢氟酸 、 水 作用下， 以 乙腈 为溶剂， 生成 methyl 1,6-dihydroxy-cyclohex-2-encarboxylate
  参考文献：
  名称：

  Enantioselective total synthesis of idesolide via NaHCO3-promoted dimerization

  摘要：

  The enantioselective total synthesis of idesolide has been accomplished in 20% overall yield from a known allylic alcohol by a nine-step sequence involving the Sharpless asymmetric epoxidation as the source of chirality and an efficient NaHCO3-promoted dimerization of the monomeric form of idesolide as the key transformation. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.05.034

文献信息

• Total Synthesis and Determination of the Absolute Configuration of (−)-Idesolide
  作者：Hiroyuki Yamakoshi、Masatoshi Shibuya、Masaki Tomizawa、Yuji Osada、Naoki Kanoh、Yoshiharu Iwabuchi

  DOI：10.1021/ol9029676

  日期：2010.3.5

  The first total synthesis of (−)-idesolide was achieved via organocatalytic, enantioselective oxidative kinetic resolution (OKR) using (1S,4S)-4-Bn-1-Bu-AZADOH- and AZADO-catalyzed dimerization of (S)-(−)-methyl 1-hydroxy-6-oxo-2-cyclohexenecarboxylate. The absolute configuration of (−)-idesolide is determined to be 2R,2′S,3aS,7aR.

  （-）-固体的第一个全合成反应是通过有机催化，对映选择性氧化动力学拆分（OKR）使用（1 S，4 S）-4-Bn-1-Bu-AZADOH-和AZADO催化的（S）二聚作用实现的-（-）-1-羟基-6-氧代-2-环己烯甲酸甲酯。（ - ） -的绝对构idesolide被确定为2 - [R，2'小号，3A小号，7α - [R 。
• Highly Efficient, Organocatalytic Aerobic Alcohol Oxidation
  作者：Masatoshi Shibuya、Yuji Osada、Yusuke Sasano、Masaki Tomizawa、Yoshiharu Iwabuchi

  DOI：10.1021/ja110940c

  日期：2011.5.4

  5- Fluoro-2-azaadamantane N-oxyl (5-FAZADO) realizes a simple, organocatalytic aerobic alcohol oxidation system that has a wide scope under mild conditions at ambient pressure and temperature and is weakly acidic and halogen- and transition-metal-free. The oxoammonium nitrate (5-F-AZADO(+)NO(3)(-)) works as a bifunctional catalyst of 5-F-AZADO and NO(x) that enables the catalytic aerobic oxidation of alcohols by itself (a metal-salt-free system).
• Safe and Scalable Aerobic Oxidation by 2-Azaadamantan-2-ol (AZADOL)/NO_<i>x</i> Catalysis: Large-Scale Preparation of Shi’s Catalyst
  作者：Yusuke Sasano、Hikaru Sato、Shinsuke Tadokoro、Masami Kozawa、Yoshiharu Iwabuchi

  DOI：10.1021/acs.oprd.8b00456

  日期：2019.4.19

  A method for safe and scalable aerobic alcohol oxidation using 2-azaadamantan-2-ol (AZADOL), an azaadamantane-type hydroxylamine catalyst, with a NOx cocatalyst in a conventional batch reactor has been developed. The use of 2 mol % AZADOL and 10 mol % NaNO2 was determined to promote aerobic alcohol oxidation quantitatively within a reasonable time (8 h). Safety is ensured by controlling the reaction temperature below the flash point of the acetic acid solvent. The robustness of the developed method is demonstrated by the SOO g scale oxidation of diacetone fructose into Shi's catalyst for asymmetric epoxidation.