erythro-2-<1-Hydroxy-1-(trimethylsilyl)ethyl>cyclohexanone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: erythro-2-<1-Hydroxy-1-(trimethylsilyl)ethyl>cyclohexanone
• 英文别名: (2S)-2-[(1R)-1-hydroxy-1-trimethylsilylethyl]cyclohexan-1-one
• 化学式: C₁₁H₂₂O₂Si
• 分子量: 214.38
• InChiKey: VZAJECMAFNWOCR-GXSJLCMTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.37
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  erythro-2-<1-Hydroxy-1-(trimethylsilyl)ethyl>cyclohexanone 在 camphor-10-sulfonic acid 、 二异丁基氢化铝 作用下， 以 二氯甲烷 为溶剂， 反应 44.0h， 生成 (Z)-2-<1-(Trimethylsilyl)ethylidene>cyclohexan-1-ol
  参考文献：
  名称：

  Novel stereocontrolled syntheses of exocyclic γ-oxovinyltrimethylsilanes. A potential route for stereodefined exocyclic tetrasubstituted alkenes

  摘要：

  δ-羟基-δ-氧代三甲基硅烷的脱水过程在很大程度上取决于生成立体选择性 (Z)- 和 (E)- δ-氧代乙烯基三irnethyl 硅烷的条件，这些硅烷是制备立体定义的外环四取代烯的潜在前体。

  DOI：

  10.1039/c39930001365
• 作为产物：
  描述：

  2-acetylcyclohexanone monoethyleneketal 在 六甲基磷酰三胺 、 水 、 4-甲基苯磺酸吡啶 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 丙酮 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 erythro-2-<1-Hydroxy-1-(trimethylsilyl)ethyl>cyclohexanone
  参考文献：
  名称：

  Novel stereocontrolled syntheses of exocyclic γ-oxovinyltrimethylsilanes. A potential route for stereodefined exocyclic tetrasubstituted alkenes

  摘要：

  δ-羟基-δ-氧代三甲基硅烷的脱水过程在很大程度上取决于生成立体选择性 (Z)- 和 (E)- δ-氧代乙烯基三irnethyl 硅烷的条件，这些硅烷是制备立体定义的外环四取代烯的潜在前体。

  DOI：

  10.1039/c39930001365

文献信息

• Novel stereocontrolled syntheses of exocyclic γ-oxovinyltrimethylsilanes. A potential route for stereodefined exocyclic tetrasubstituted alkenes
  作者：Kazuhiko Nakatani、Tomoko Izawa、Yoshihiko Odagaki、Sachihiko Isoe

  DOI：10.1039/c39930001365

  日期：——

  The course of the dehydration of α-hydroxy-γ-oxotrimethylsilanes is highly dependent on the conditions to produce stereoselectively (Z)- and (E)-γ-oxovinyltrirnethylsilanes, which are potential precursors for preparation of stereodefined exocyclic tetrasubstituted alkenes.

  δ-羟基-δ-氧代三甲基硅烷的脱水过程在很大程度上取决于生成立体选择性 (Z)- 和 (E)- δ-氧代乙烯基三irnethyl 硅烷的条件，这些硅烷是制备立体定义的外环四取代烯的潜在前体。
• Syntheses and Theoretical Studies of Exocyclic .gamma.-Oxoalkenyltrimethylsilanes. An Approach to the Stereodefined Exocyclic Tetrasubstituted Alkenes
  作者：Kazuhiko Nakatani、Tomoko Izawa、Sachihiko Isoe

  DOI：10.1021/jo00099a027

  日期：1994.10

  The Z-selectivity in the dehydration of alpha-hydroxy-gamma-oxoalkyltrimethylsilanes under acidic conditions was studied from experimental and theoretical points of view. Experimental results showed that (Z)-gamma-oxoalkenyltrimethylsilanes were thermodynamic products under these conditions. The dehydration studies of the compound involving the tert-butyl group instead of the TMS group pointed out that not only steric but also electronic effects of Si could contribute to the distribution of the products as well as their stereochemistries. Theoretical studies using ab initio calculation at the 6-31G* level indicated that the (Z)-isomer was thermodynamically more stable than the corresponding (E)-isomer. Detail examinations of the optimized structures showed that the configuration of Si in the (Z)-isomer was slightly distorted from tetrahedral. Interpretation of the geometrical change of Si to rationalization of the thermodynamic preference was discussed fi om the viewpoint of possible coordination of the carbonyl oxygen to Si. Those (Z)-gamma-oxoalkenyltrimethylsilanes would have potential to be the novel type of alkenylmetal compounds in organic synthesis as we demonstrated in the construction of stereodefined exocyclic tetrasubstituted alkene.