(3R,4S,5R)-3,4,5-trimethyloxolan-2-one | 53155-65-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3R,4S,5R)-3,4,5-trimethyloxolan-2-one
• CAS: 53155-65-0；53155-66-1；53155-67-2；53155-68-3；85564-78-9；104110-09-0；104110-10-3；104110-11-4；104110-12-5
• 化学式: C₇H₁₂O₂
• 分子量: 128.171
• InChiKey: JZIORVLQWOYSTQ-KVQBGUIXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  N,N-diisopropyl-E-2,3-dimethylpent-3-enamide 在 9-borabicyclo[3.3.1]nonane dimer 、 硫酸 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 生成 (3R,4S,5R)-3,4,5-trimethyloxolan-2-one
  参考文献：
  名称：

  Diastereoselective Osmylation and Hydroboration of β,γ-Unsaturated N,N-Diisopropylamides and Acid-Catalyzed Conversion to δ-Lactones

  摘要：

  The title reactions of beta,gamma-unsaturated N,N-diisopropylamides occur with useful diastereofacial selectivity. The major diol isomer from osmylation of alkenes 1, 10, 11, and 12 in the presence of TMEDA at -78 degrees C corresponds to the facial preference shown in transition state model 41 (R-z = H), while the opposite preference for 42 is observed with the Z-alkene 13. (Table 1). Hydroboration with g-BBN does not show this inversion of diastereofacial selectivity for the Z-alkene. All of the results in Table 2 correspond to the usual preference for a transition state such as 45. Acid-catalyzed lactonization of the alcohols obtained in Tables 1 and 2 can be carried out with overall retention of configuration to afford delta-lactones. Butenolide 5 was prepared with 90% se from alcohol 2a via osmylation followed by acid-catalyzed lactonization to 3 and elimination using SOCl2/pyridine.

  DOI：

  10.1021/jo990119u

文献信息

• Stereoselective Enzyme Cascades: An Efficient Synthesis of Chiral γ-Butyrolactones
  作者：Thomas Classen、Margarete Korpak、Melanie Schölzel、Jörg Pietruszka

  DOI：10.1021/cs5000262

  日期：2014.5.2

  A one-pot consecutive two-enzyme sequential cascade toward chiral γ-butyrolactones using an enoate reductase as well as alcohol dehydrogenases in combination with a glucose dehydrogenase is reported. In this scalable process, the products were obtained in high yield (up to 90%) and with perfect enantioselectivity (98→99% ee). The starting materials, ethyl 4-oxo-pent-2-enoates, are readily accessible

  报道了使用烯醇酸还原酶以及醇脱氢酶与葡萄糖脱氢酶的组合，向手性γ-丁内酯的一锅连续二酶顺序级联。在这种可扩展的过程中，以高收率（高达90％）和完美的对映选择性（98→99％ee）获得了产品。起始原料4-氧代-戊-2-烯酸乙酯很容易通过Wittig型反应获得。此外，已对烯酸还原酶催化反应的立体选择性进行了详细研究，从而使人们对该酶的机理有了更深入的认识。
• Chiral discrimination in the reactions of the enolate E-[(η5-C5H5)Fe(CO)(PPh3)COCHMe]−Li+ with and but-2-ene oxides in the presence of BF3·OEt3
  作者：Stephen G. Davies、Peter Warner

  DOI：10.1016/s0040-4039(00)94959-1

  日期：1985.1
• Diastereoselective Osmylation and Hydroboration of β,γ-Unsaturated <i>N,N</i>-Diisopropylamides and Acid-Catalyzed Conversion to δ-Lactones
  作者：E. Vedejs、A. W. Kruger

  DOI：10.1021/jo990119u

  日期：1999.6.1

  The title reactions of beta,gamma-unsaturated N,N-diisopropylamides occur with useful diastereofacial selectivity. The major diol isomer from osmylation of alkenes 1, 10, 11, and 12 in the presence of TMEDA at -78 degrees C corresponds to the facial preference shown in transition state model 41 (R-z = H), while the opposite preference for 42 is observed with the Z-alkene 13. (Table 1). Hydroboration with g-BBN does not show this inversion of diastereofacial selectivity for the Z-alkene. All of the results in Table 2 correspond to the usual preference for a transition state such as 45. Acid-catalyzed lactonization of the alcohols obtained in Tables 1 and 2 can be carried out with overall retention of configuration to afford delta-lactones. Butenolide 5 was prepared with 90% se from alcohol 2a via osmylation followed by acid-catalyzed lactonization to 3 and elimination using SOCl2/pyridine.