(5R*,6S*)-5,6-bis(tert-butyldimethylsilyloxy)cyclooctene

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (5R*,6S*)-5,6-bis(tert-butyldimethylsilyloxy)cyclooctene
• 英文别名: tert-butyl-[(1R,4Z,8S)-8-[tert-butyl(dimethyl)silyl]oxycyclooct-4-en-1-yl]oxy-dimethylsilane
• 化学式: C₂₀H₄₂O₂Si₂
• 分子量: 370.723
• InChiKey: VEIXMJMHUCEXPT-YSLLNQIKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (5R*,6S*)-5,6-bis(tert-butyldimethylsilyloxy)cyclooctene 在 platinum(IV) oxide 、 四氧化锇 sodium periodate 、 氢气 、 sodium hydride 、 N-甲基吗啉氧化物 作用下， 以 四氢呋喃 、 水 、 乙酸乙酯 、 丙酮 、 苯 为溶剂， 反应 17.5h， 生成 dimethyl (6R,7S)-6,7-bis[[tert-butyl(dimethyl)silyl]oxy]dodecanedioate
  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：

  1,5-cis,cis-cyclooctadiene 在 咪唑 、 四氧化锇 、 N-甲基吲哚酮 、 水 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 34.0h， 生成 (5R*,6S*)-5,6-bis(tert-butyldimethylsilyloxy)cyclooctene
  参考文献：
  名称：

  Functionalised bicyclic alcohols by enantioselective α-deprotonation–rearrangement of meso-epoxides†

  摘要：

  使用手性的（-）-鹰爪豆碱3或（-）-α-异鹰爪豆碱4作为催化剂，在有机锂试剂存在下，对非手性的取代环辛烯氧化物7、27和28以及N-Boc六氢吖啶酮氧化物45进行对映选择性的α-脱质子化-重排反应，可以得到功能化的双环[3.3.0]辛-2-醇9、29和32以及吲哚兹啶醇47，产率为50-72%，对映体过量率为83-89% ee。

  DOI：

  10.1039/b105369h

文献信息

• Functionalized Bicyclo[3.3.0]octanes by Enantioselective Transannular Desymmetrization
  作者：David M. Hodgson、Iain D. Cameron

  DOI：10.1021/ol006947n

  日期：2001.2.1

  alpha-deprotonation-rearrangement of achiral substituted cyclooctene oxides 7, 17, and 18 using organolithiums in the presence of (-)-sparteine (3) or (-)-alpha-isosparteine (4) gives the functionalized bicyclo[3.3.0]octan-2-ols 8, 19, and 20 in 56-72% yields and 83-89% ee's.

  [图：见正文]在（-）-天冬氨酸（3）或（-）-α-异天冬氨酸（4）存在下，使用有机锂对非手性取代的环辛烯氧化物7、17和18进行对映选择性α-去质子重排功能化的双环[3.3.0] octan-2-ols 8、19和20的产率为56-72％，ee为83-89％。
• Functionalised bicyclic alcohols by enantioselective α-deprotonation–rearrangement of meso-epoxides†
  作者：David M. Hodgson、Iain D. Cameron、Martin Christlieb、Rebecca Green、Gary P. Lee、Lesley A. Robinson

  DOI：10.1039/b105369h

  日期：——

  Enantioselective α-deprotonation–rearrangement of achiral substituted cyclooctene oxides 7, 27 and 28 and N-Boc hexahydroazonine oxide 45 using organolithiums in the presence of (−)-sparteine 3 or (−)-α-isosparteine 4 gives the functionalised bicyclo[3.3.0]octan-2-ols 9, 29, and 32 and indolizinol 47 in 50–72% yields and 83–89% ees.

  使用手性的（-）-鹰爪豆碱3或（-）-α-异鹰爪豆碱4作为催化剂，在有机锂试剂存在下，对非手性的取代环辛烯氧化物7、27和28以及N-Boc六氢吖啶酮氧化物45进行对映选择性的α-脱质子化-重排反应，可以得到功能化的双环[3.3.0]辛-2-醇9、29和32以及吲哚兹啶醇47，产率为50-72%，对映体过量率为83-89% ee。
• 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.