(E/Z)-5-(trimethylsilyl)adamantan-2-ol | 942118-84-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E/Z)-5-(trimethylsilyl)adamantan-2-ol
• 英文别名: 5-trimethylsilyladamantan-2-ol
• CAS: 942118-84-5
• 化学式: C₁₃H₂₄OSi
• 分子量: 224.418
• InChiKey: LIXARIJLVCQSER-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.27
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E/Z)-5-(trimethylsilyl)adamantan-2-ol 在 氢氧化钾 、 三氟乙酸 作用下， 生成 5-trimethylsilyladamantan-2-ol
  参考文献：
  名称：

  Gas-Phase Diastereoselectivity of Secondary 5-Substituted (X)-Adamant-2-yl (X = F, Si(CH₃)₃) Cations

  摘要：

  Secondary 5-X-adamant-2-yl cations I-X (X = F, Si(CH3)(3)) have been generated in the gas phase (total pressure = 760 Torr) from protonation-induced defluorination of epimeric 2-F-5-X-adamantanes 1(X) and their kinetic diastereoselectivity toward (CH3OH)-O-18 investigated in the 40-160 degrees C range. The experimental results indicate that the facial selectivity of I-X is insensitive to the composition of the starting 1(X) epimers as well as to the presence and the concentration of a powerful base (N(C2H5)(3)). This kinetic picture, supported by B3LYP/6-31G* calculations, is consistent with a single stable pyramidalized structure for I-X, that is, (Z)-5-F-adamant-2-yl (I-F(Z)) and (E)-5-Si(CH3)(3)-adamant-2-yl cations (I-Si(E)). The temperature dependence of the I-X diastereoselectivity lends support to the intermediacy of noncovalent adducts [(IXCH3OH)-C-.-O-18], characterized by a specific C2-(H+...O18)(H)CH3 hydrogen bonding interaction. Their conversion to the covalently bonded O-methylated (Z)- (IIXZ) and (E)-5-X-adamantan-2-ols (IIXE; X = F, Si(CH3)(3)) is governed by activation parameters, whose magnitude depends on the specific I-X face accommodating (CH3OH)-O-18. The gas-phase diastereoselectivity of I-X toward (CH3OH)-O-18 is compared to that exhibited in related gas-phase and solution processes. The emerging picture indicates that the factors determining the diastereoselectivity of I-X toward simple nucleophiles in the gaseous and condensed media are completely different.

  DOI：

  10.1021/jo0702140
• 作为产物：
  描述：

  5-(trimethylsilyl)adamantan-2-one 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 生成 (E/Z)-5-(trimethylsilyl)adamantan-2-ol
  参考文献：
  名称：

  Transmission of polar substituent effects in the adamantane ring system as monitored by 19F NMR: hyperconjugation as a stereoinductive factor

  摘要：

  A limited series of (E)- and (Z)-5-substituted adamant-2-yl fluorides 8 and 9, respectively, has been synthesized and characterized, and the F-19 chemical shifts have been measured in several solvents. A wide range of F-19 substituent chemical shifts (SCS, ppm) are obtained for the former system (ca. 9.1 (c-C6H12), 9.6 (CDCl3), and 11.8 (HFIP)) compared to the latter (ca. 0.6 (c-C6H12), 0.7 (CDCl3), and 2.3 (HFIP)). Factorization of the F-19 SCS into polar field (rho-F-sigma-F) and residual contributions (F-19 SCS - rho-F-sigma-F) reveals the predominance of the latter solvent-independent component for the E fluorides (8). Comparison of 8 with a similar dissection of the F-19 SCS of 4-substituted bicyclo[2.2.2]oct-1-yl fluorides 2 strongly suggests that the origin of the large residual contributions for 8 is "through-three-bond" electron delocalization or double hyperconjugation. The importance of this long-range electronic mechanism as a factor governing pi-facial diastereoselection in 2,5-disubstituted adamantanes (1) is discussed. In particular, the assertion that the p-anilino substituent is an electron donor group at remote probe or reaction sites in saturated systems is addressed.

  DOI：

  10.1021/jo00010a012

文献信息

• Gas-Phase Diastereoselectivity of Secondary 5-Substituted (X)-Adamant-2-yl (X = F, Si(CH₃)₃) Cations
  作者：Caterina Fraschetti、Francesca R. Novara、Antonello Filippi、Neil A. Trout、William Adcock、Ted S. Sorensen、Maurizio Speranza

  DOI：10.1021/jo0702140

  日期：2007.5.1

  Secondary 5-X-adamant-2-yl cations I-X (X = F, Si(CH3)(3)) have been generated in the gas phase (total pressure = 760 Torr) from protonation-induced defluorination of epimeric 2-F-5-X-adamantanes 1(X) and their kinetic diastereoselectivity toward (CH3OH)-O-18 investigated in the 40-160 degrees C range. The experimental results indicate that the facial selectivity of I-X is insensitive to the composition of the starting 1(X) epimers as well as to the presence and the concentration of a powerful base (N(C2H5)(3)). This kinetic picture, supported by B3LYP/6-31G* calculations, is consistent with a single stable pyramidalized structure for I-X, that is, (Z)-5-F-adamant-2-yl (I-F(Z)) and (E)-5-Si(CH3)(3)-adamant-2-yl cations (I-Si(E)). The temperature dependence of the I-X diastereoselectivity lends support to the intermediacy of noncovalent adducts [(IXCH3OH)-C-.-O-18], characterized by a specific C2-(H+...O18)(H)CH3 hydrogen bonding interaction. Their conversion to the covalently bonded O-methylated (Z)- (IIXZ) and (E)-5-X-adamantan-2-ols (IIXE; X = F, Si(CH3)(3)) is governed by activation parameters, whose magnitude depends on the specific I-X face accommodating (CH3OH)-O-18. The gas-phase diastereoselectivity of I-X toward (CH3OH)-O-18 is compared to that exhibited in related gas-phase and solution processes. The emerging picture indicates that the factors determining the diastereoselectivity of I-X toward simple nucleophiles in the gaseous and condensed media are completely different.
• Transmission of polar substituent effects in the adamantane ring system as monitored by 19F NMR: hyperconjugation as a stereoinductive factor
  作者：William Adcock、Neil A. Trout

  DOI：10.1021/jo00010a012

  日期：1991.5

  A limited series of (E)- and (Z)-5-substituted adamant-2-yl fluorides 8 and 9, respectively, has been synthesized and characterized, and the F-19 chemical shifts have been measured in several solvents. A wide range of F-19 substituent chemical shifts (SCS, ppm) are obtained for the former system (ca. 9.1 (c-C6H12), 9.6 (CDCl3), and 11.8 (HFIP)) compared to the latter (ca. 0.6 (c-C6H12), 0.7 (CDCl3), and 2.3 (HFIP)). Factorization of the F-19 SCS into polar field (rho-F-sigma-F) and residual contributions (F-19 SCS - rho-F-sigma-F) reveals the predominance of the latter solvent-independent component for the E fluorides (8). Comparison of 8 with a similar dissection of the F-19 SCS of 4-substituted bicyclo[2.2.2]oct-1-yl fluorides 2 strongly suggests that the origin of the large residual contributions for 8 is "through-three-bond" electron delocalization or double hyperconjugation. The importance of this long-range electronic mechanism as a factor governing pi-facial diastereoselection in 2,5-disubstituted adamantanes (1) is discussed. In particular, the assertion that the p-anilino substituent is an electron donor group at remote probe or reaction sites in saturated systems is addressed.