(1,6,7-trioxaspiro[4.5]dec-8-yl)acetyc acid benzyl ester | 854307-34-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1,6,7-trioxaspiro[4.5]dec-8-yl)acetyc acid benzyl ester
• 英文别名: Benzyl 2-(1,6,7-trioxaspiro[4.5]decan-8-yl)acetate
• CAS: 854307-34-9
• 化学式: C₁₆H₂₀O₅
• 分子量: 292.332
• InChiKey: ZSHRCQGNRJYQIX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1,6,7-trioxaspiro[4.5]dec-8-yl)acetyc acid benzyl ester 在 锂硼氢 作用下， 以 乙醚 为溶剂， 反应 0.85h， 以89%的产率得到2-(1,6,7-trioxaspiro[4.5]dec-8-yl)ethanol
  参考文献：
  名称：

  On the Susceptibility of Organic Peroxy Bonds to Hydride Reduction

  摘要：

  Reduction of organic molecules that contain a peroxy bond is broadly considered as a "risky" and uncertain operation when cleavage of the peroxy linkage is not desired. For this reason, such reduction steps are normally avoided at the planning stage of the synthesis when possible. As a natural consequence, the information in the literature about the susceptibility of organic peroxy bonds to reducing species is scant. In this work the tolerance of organic peroxy bonds to some common hydride reductants was examined systematically for the first time. Using reduction of ester group to alcohol as a probe, LiAlH4, LiAlH((OBU)-B-t)(3), LiBHEt3, and LiBH4 were found to be significantly better than other reductants examined when taking into consideration both the completeness of the reduction of ester groups and the peroxy bond survival rate. LiBH4 appeared to be the most suitable reductant for the reduction under discussion, not only because of the high reduction yields/excellent compatibility with peroxy bonds, but also because of the advantages in practical aspects. The results disclosed herein may (hopefully) provide a handy reference for dealing with reduction of other peroxy bond-containing molecules in the future.

  DOI：

  10.1021/jo050139y
• 作为产物：
  描述：

  (E)-5-[2-(3-Methoxymethoxy-propyl)-[1,3]dithian-2-yl]-pent-2-enoic acid benzyl ester 在 盐酸 、 2,2,2-三氟乙醇 、 对甲苯磺酸 、 二乙胺 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 24.5h， 生成 (1,6,7-trioxaspiro[4.5]dec-8-yl)acetyc acid benzyl ester
  参考文献：
  名称：

  1,6,7-三氧杂螺环[4.5]癸烷的合成

  摘要：

  作为潜在的抗疟药，设计并合成了四种新颖的螺过氧化物，并使用小林的方法（经过修改）引入了过氧键。结果表明，通过使用环状半缩酮作为底物，可以在不依赖昂贵的Sc（OTf）3催化剂的情况下以高收率实现氢过氧基的结合。

  DOI：

  10.1016/j.tetlet.2005.06.110

文献信息

• Design, synthesis and in vitro antimalarial activity of spiroperoxides
  作者：Hong-Xia Jin、Qi Zhang、Hye-Sook Kim、Yusuke Wataya、He-Hua Liu、Yikang Wu

  DOI：10.1016/j.tet.2006.05.065

  日期：2006.8

  group. When the electron-withdrawing group in the Michael acceptor was a nitro group, the closure of the peroxy ring occurred readily under the hydroxidation conditions. Presence of a benzene ring fused to the peroxy ring effectively reduced the degrees of freedom in the transition state for the ring-closure step and made the otherwise very difficult seven-membered 1,2-dioxepane rather easy to form

  设计和合成了几种螺过氧抗疟疾化合物，使用过氧化氢在UHP中（脲-H 2 O 2络合物）作为过氧键的来源。掺入H 2 O 2在当前情况下，由于在酮羰基上存在羟基γ或δ，形成五元或六元环状半缩酮的可能性极大地促进了通过缩酮交换反应进入有机分子骨架。当迈克尔受体中的吸电子基团是硝基时，在水氧化条件下，过氧环的闭合很容易发生。与过氧环稠合的苯环的存在有效地降低了闭环步骤过渡态的自由度，并使原本非常困难的七元1,2-二氧戊环很容易通过分子内迈克尔加成而形成。
• On the Susceptibility of Organic Peroxy Bonds to Hydride Reduction
  作者：Hong-Xia Jin、He-Hua Liu、Qi Zhang、Yikang Wu

  DOI：10.1021/jo050139y

  日期：2005.5.1

  Reduction of organic molecules that contain a peroxy bond is broadly considered as a "risky" and uncertain operation when cleavage of the peroxy linkage is not desired. For this reason, such reduction steps are normally avoided at the planning stage of the synthesis when possible. As a natural consequence, the information in the literature about the susceptibility of organic peroxy bonds to reducing species is scant. In this work the tolerance of organic peroxy bonds to some common hydride reductants was examined systematically for the first time. Using reduction of ester group to alcohol as a probe, LiAlH4, LiAlH((OBU)-B-t)(3), LiBHEt3, and LiBH4 were found to be significantly better than other reductants examined when taking into consideration both the completeness of the reduction of ester groups and the peroxy bond survival rate. LiBH4 appeared to be the most suitable reductant for the reduction under discussion, not only because of the high reduction yields/excellent compatibility with peroxy bonds, but also because of the advantages in practical aspects. The results disclosed herein may (hopefully) provide a handy reference for dealing with reduction of other peroxy bond-containing molecules in the future.
• Synthesis of 1,6,7-trioxa-spiro[4.5]decanes
  作者：Hong-Xia Jin、He-Hua Liu、Qi Zhang、Yikang Wu

  DOI：10.1016/j.tetlet.2005.06.110

  日期：2005.8

  As potential antimalarial agents, four novel spiro-peroxides were designed and synthesized with the peroxy bond introduced employing the Kobayashi’s methodology (with modifications). The results showed that by using cyclic hemiketal as substrates the incorporation of the hydroperoxyl group could be achieved in high yields without recourse to the expensive Sc(OTf)3 catalyst.

  作为潜在的抗疟药，设计并合成了四种新颖的螺过氧化物，并使用小林的方法（经过修改）引入了过氧键。结果表明，通过使用环状半缩酮作为底物，可以在不依赖昂贵的Sc（OTf）3催化剂的情况下以高收率实现氢过氧基的结合。