Methyl (+/-)-2-hydroxy-3-(2-methyl-1,3-dioxolan-2-yl)propanoate | 163458-23-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Methyl (+/-)-2-hydroxy-3-(2-methyl-1,3-dioxolan-2-yl)propanoate
• 英文别名: Methyl 2-hydroxy-3-(2-methyl-1,3-dioxolan-2-yl)propanoate
• CAS: 163458-23-9
• 化学式: C₈H₁₄O₅
• 分子量: 190.196
• InChiKey: QVAUIXNYNGKWLB-UHFFFAOYSA-N

物化性质

• 沸点：
  266.8±20.0 °C(Predicted)
• 密度：
  1.180±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Methyl (+/-)-2-hydroxy-3-(2-methyl-1,3-dioxolan-2-yl)propanoate 在 aluminum oxide 、 钌 氢气 、 对甲苯磺酸 作用下， 以 异丙醇 、 丙酮 为溶剂， 40.0~60.0 ℃ 、4.0 MPa 条件下， 反应 11.0h， 生成 5-甲基-3-羟基二氢呋喃-2(3H)-酮
  参考文献：
  名称：

  Synthesis of α-hydroxy-γ-butyrolactones from acrylates and 1,3-dioxolanes using N-hydroxyphthalimide (NHPI) as a key catalyst

  摘要：

  A new route to alpha-hydroxy-gamma-butyrolactones through three-component radical coupling of 1,3-dioxoranes, acrylates, and molecular oxygen using N-hydroxyphthalimide (NHPI) as a key catalyst has been developed. For example, the addition of 1,3dioxarane to methyl acrylate under dioxygen by NHPI followed by catalytic hydrogenation of the resulting adduct on Pd/C afforded alpha-hydroxy-gamma-butyrolactone in good yield. This method provides a facile approach to alpha-hydroxy-gamma-butyrolactones, which are difficult to synthesize by conventional methods. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.03.137
• 作为产物：
  描述：

  2-甲基-1,3-二氧戊环 、 丙烯酸甲酯（MA） 在 N-羟基邻苯二甲酰亚胺 、 cobalt(II) acetate 氧气 作用下， 反应 3.0h， 以81%的产率得到Methyl (+/-)-2-hydroxy-3-(2-methyl-1,3-dioxolan-2-yl)propanoate
  参考文献：
  名称：

  N-羟基邻苯二甲酰亚胺催化的 1,3-二氧戊环和分子氧在环境条件下自由基加成烯烃：β-氧羰基化合物的新途径

  摘要：

  已经开发了一种使用 1,3-二氧戊环和分子氧的烯烃催化羟基酰化反应，并在催化量的 NHPI 和 Co(OAc) 存在下，在双氧气氛下与丙烯酸甲酯反应。 )2 以 81% 的产率产生相应的加合物。

  DOI：

  10.1039/b008418m

文献信息

• N-Hydroxyphthalimide-catalyzed radical addition of 1,3-dioxolanes and molecular oxygen to alkenes under ambient conditions: a new route to β-oxycarbonyl compounds
  作者：Kazutaka Hirano、Takahiro Iwahama、Satoshi Sakaguchi、Yasutaka Ishii

  DOI：10.1039/b008418m

  日期：——

  A novel catalytic hydroxyacylation of alkenes using 1,3-dioxolanes and molecular oxygen has been developed, and the reaction of 2-methyl-1,3-dioxolane with methyl acrylate under dioxygen atmosphere in the presence of catalytic amounts of NHPI and Co(OAc)2 produced the corresponding adduct in 81% yield.

  已经开发了一种使用 1,3-二氧戊环和分子氧的烯烃催化羟基酰化反应，并在催化量的 NHPI 和 Co(OAc) 存在下，在双氧气氛下与丙烯酸甲酯反应。 )2 以 81% 的产率产生相应的加合物。
• Synthesis of (+)- and (-)-N-BOC-7-Azabicyclo[2.2.1]heptan-2-ones, Versatile Intermediates for the Enantiospecific Synthesis of (+)- and (-)-Epibatidine and Analogs
  作者：Andres Hernandez、Manuel Marcos、Henry Rapoport

  DOI：10.1021/jo00114a015

  日期：1995.5

  (+)- and (-)-Epibatidine, nonopiate antinociceptive alkaloids, have been prepared from (-)- and (+)-N-BOC-7-azabicyclo[2.2.1]heptan-2-one which were produced by resolution of the racemic mixture of the corresponding alcohols obtained in the previous racemic synthesis. In the present work, we report the enantiospecific synthesis of(-)- and (+)-N-BOC-7-azabicyclo[2.2.1]heptan-2-one from L-glutamic acid and levulinic acid. Also, this report describes the selective formation of trans-2,3-disubstituted-7-azabicyclo[2.2.1]heptanes from N-benzyl-5-(1'-methoxycarbonyl-3'-oxobutyl)proline via a decarbonylation/iminium ion cyclization process. These functionalized intermediates are of potential value for the enantiospecific synthesis of epibatidine analogues.

  (+)-和(-)-表瑟啶（(+)-和(-)-Epibatidine），作为非阿片类抗痛觉碱基，在本研究中已由(-)-和(+)-N-BOC-7-氮杂双环[2.2.1]庚烷-2-酮合成。这些酮类化合物是通过对相应光学活性醇类的消旋混合物进行拆分而获得的，之前的研究已实现该消旋合成。在本研究中，我们报告了通过L-谷氨酸和戊二酸（levulinic acid）对映选择性合成(-)-和(+)-N-BOC-7-氮杂双环[2.2.1]庚烷-2-酮的方法。此外，本报告还描述了通过N-苯甲基-5-(1'-甲氧基羰基-3'-氧代丁基)脯氨酸，经脱羰/亚胺离子环化过程选择性制备反式-2,3-二取代-7-氮杂双环[2.2.1]庚烷的过程。这些功能化中间体在表瑟啶类似物的对映选择性合成中具有潜在价值。
• Synthesis of α-hydroxy-γ-butyrolactones from acrylates and 1,3-dioxolanes using N-hydroxyphthalimide (NHPI) as a key catalyst
  作者：Takashi Kagayama、Satoshi Sakaguchi、Yasutaka Ishii

  DOI：10.1016/j.tetlet.2005.03.137

  日期：2005.5

  A new route to alpha-hydroxy-gamma-butyrolactones through three-component radical coupling of 1,3-dioxoranes, acrylates, and molecular oxygen using N-hydroxyphthalimide (NHPI) as a key catalyst has been developed. For example, the addition of 1,3dioxarane to methyl acrylate under dioxygen by NHPI followed by catalytic hydrogenation of the resulting adduct on Pd/C afforded alpha-hydroxy-gamma-butyrolactone in good yield. This method provides a facile approach to alpha-hydroxy-gamma-butyrolactones, which are difficult to synthesize by conventional methods. (c) 2005 Elsevier Ltd. All rights reserved.
• Anthrone-derived NHPI analogues as catalysts in reactions using oxygen as an oxidant
  作者：Juan Shen、Choon-Hong Tan

  DOI：10.1039/b812351a

  日期：——

  An enantioselective synthesis of anthrone-derived NHPI analogues has been developed. One of these analogues, in combination with Co salts, was employed to catalyse the aerobic oxidation of benzylic compounds and diols. Exploratory studies using a racemic version of the catalyst were also conducted. Radical addition of dioxolanes or alcohols to activated alkenes with molecular oxygen as the terminal oxidant was also shown to be catalysed with NHPI analogues.

  已开发出一种对映选择性的合成龙脑衍生的NHPI类似物。其中一种类似物与钴盐结合，应用于催化苄基化合物和二醇的好氧氧化。还进行了使用催化剂的外消旋版本进行的探索性研究。还证明了用分子氧作为终端氧化剂，二氧六烷或醇对活化烯烃的自由基加成也可由NHPI类似物催化。