(2R*,3S*)-3-(Allyloxy)-2-<2'-(2'',2''-dimethyl-1'',3''-dioxolan-4''-yl)ethyl>oxepane

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: (2R*,3S*)-3-(Allyloxy)-2-<2'-(2'',2''-dimethyl-1'',3''-dioxolan-4''-yl)ethyl>oxepane
• 英文别名: (2R,3S)-2-[2-(2,2-dimethyl-1,3-dioxolan-4-yl)ethyl]-3-prop-2-enoxyoxepane
• 化学式: C₁₆H₂₈O₄
• 分子量: 284.396
• InChiKey: ZRVPXOQVBVYQLV-NOYMGPGASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R*,3S*)-3-(Allyloxy)-2-<2'-(2'',2''-dimethyl-1'',3''-dioxolan-4''-yl)ethyl>oxepane 在 camphor-10-sulfonic acid 作用下， 以 甲醇 为溶剂， 反应 0.25h， 以95%的产率得到(2'R*,3'S*)-4-<3'-(Allyloxy)oxepan-2'-yl>-1,2-butanediol
  参考文献：
  名称：

  Simple Designs for the Construction of Complex trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations

  摘要：

  A successful design for the construction of trans-fused medium-size cyclic ethers is described. The key features of the synthesis are as follows: (i) intramolecular oxirane ring expansion in cycloalkenes to give bridged oxabicyclic systems and (ii) linear, one- or two-directional synthetic operations which generate external oxocycles in single reaction steps. The general approach involves the intramolecular addition of a stable gamma-alkoxy-substituted allylstannane to an aldehyde carbonyl group, and the entire reaction is conducted in a one-pot process which includes the following: (i) vic-diol fragmentation from the bridged oxabicyclic precursor and (ii) Lewis acid-induced cyclization of the resulting aldehyde-allylic tin system. While the present strategy was mostly developed around racemic models, the potential for adoption of;enantioselective features is immediate. The versatility, scope, limitations, and potential applications of the present technology are discussed in detail.

  DOI：

  10.1021/jo00089a034
• 作为产物：
  描述：

  4-(2,2-dimethyl-1,3-dioxolane-4-yl)-1-butanol 在 四氧化锇 咪唑 、 sodium tetrahydroborate 、 sodium periodate 、 偶氮二异丁腈 、 camphor-10-sulfonic acid 、 四丁基氟化铵 、 水 、 碘 、 sodium hydride 、 N-甲基吗啉氧化物 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 苯 为溶剂， 反应 24.92h， 生成 (2R*,3S*)-3-(Allyloxy)-2-<2'-(2'',2''-dimethyl-1'',3''-dioxolan-4''-yl)ethyl>oxepane
  参考文献：
  名称：

  Simple Designs for the Construction of Complex trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations

  摘要：

  A successful design for the construction of trans-fused medium-size cyclic ethers is described. The key features of the synthesis are as follows: (i) intramolecular oxirane ring expansion in cycloalkenes to give bridged oxabicyclic systems and (ii) linear, one- or two-directional synthetic operations which generate external oxocycles in single reaction steps. The general approach involves the intramolecular addition of a stable gamma-alkoxy-substituted allylstannane to an aldehyde carbonyl group, and the entire reaction is conducted in a one-pot process which includes the following: (i) vic-diol fragmentation from the bridged oxabicyclic precursor and (ii) Lewis acid-induced cyclization of the resulting aldehyde-allylic tin system. While the present strategy was mostly developed around racemic models, the potential for adoption of;enantioselective features is immediate. The versatility, scope, limitations, and potential applications of the present technology are discussed in detail.

  DOI：

  10.1021/jo00089a034

文献信息

• Simple Designs for the Construction of Complex trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations
  作者：Eleuterio Alvarez、Maria T. Diaz、Ricardo Perez、Jose L. Ravelo、Alicia Regueiro、Jose A. Vera、Dacil Zurita、Julio D. Martin

  DOI：10.1021/jo00089a034

  日期：1994.5

  A successful design for the construction of trans-fused medium-size cyclic ethers is described. The key features of the synthesis are as follows: (i) intramolecular oxirane ring expansion in cycloalkenes to give bridged oxabicyclic systems and (ii) linear, one- or two-directional synthetic operations which generate external oxocycles in single reaction steps. The general approach involves the intramolecular addition of a stable gamma-alkoxy-substituted allylstannane to an aldehyde carbonyl group, and the entire reaction is conducted in a one-pot process which includes the following: (i) vic-diol fragmentation from the bridged oxabicyclic precursor and (ii) Lewis acid-induced cyclization of the resulting aldehyde-allylic tin system. While the present strategy was mostly developed around racemic models, the potential for adoption of;enantioselective features is immediate. The versatility, scope, limitations, and potential applications of the present technology are discussed in detail.