5-(trimethylsilyl)adamantan-2-one | 121498-04-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-(trimethylsilyl)adamantan-2-one
• 英文别名: 5-trimethylsilyladamantan-2-one
• CAS: 121498-04-2
• 化学式: C₁₃H₂₂OSi
• 分子量: 222.403
• InChiKey: GTUZXBPERKBZEN-UHFFFAOYSA-N

物化性质

• 沸点：
  282.2±33.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.47
• 重原子数：
  15.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  5-(trimethylsilyl)adamantan-2-one 在 氨 、 hydroxylamine-O-sulfonic acid 作用下， 以 甲醇 为溶剂， 以43%的产率得到4-azi-1-(trimethylsilyl)-adamantane
  参考文献：
  名称：

  γ-取代的金刚烷内酯的分子内和分子间反应选择性

  摘要：

  进行了具有γ-取代基（R）的金刚烷亚烃类的研究，以评估位于远端的官能团的诱导和空间效应如何影响分子内和分子间产物的选择性。3 H-二嗪嗪被热解或光解以生成相应的卡宾。在快速加热下，通过分子内的1,3-CH插入将生成的碳烯异构化为2,4-二氢加金刚烷。当R是电子供体（R D）时，大多数会生成不对称的1取代衍生物，但是当R是电子受体（R A时））形成对称的7位取代基。当溶液暴露于UV-A光线下时，由羧甲基和溶剂形成的分子间加合物以较少量的分子内产物为主。3 H-重氮基的价异构化也提供了重氮化合物。在甲醇中，重氮化合物的质子化作用产生相应的2-金刚烷基阳离子时，其偶联作用超过了。富马腈通过捕集重氮化合物来控制这种转移。该加合物具有大多抗与R = R构型d和顺式，其中R = R安排甲。之间的连接如和-抗-产物的形成，并且的小号-与顺式-products被认为是两个截然不同的卡宾构象之间的快速平衡的

  DOI：

  10.1021/jo202132c
• 作为产物：
  描述：

  5-羟基-2-金刚烷酮 在 盐酸 、 氢溴酸 、 甲基锂 、 对甲苯磺酸 作用下， 以 甲醇 、 六甲基磷酰三胺 、 乙醚 、 甲苯 为溶剂， 生成 5-(trimethylsilyl)adamantan-2-one
  参考文献：
  名称：

  Reversal of Diastereoselectivities in Intra- and Intermolecular Reactions of 2-Adamantanylidenes Primarily Caused by Electron-Donating and Electron- Withdrawing Substituents on C5

  摘要：

  A reversal of diastereoselectivity was observed for novel 5-(trimethylsilyl)adamantan-2-ylidene (1c) with regard to 5-hydroxyadamantan-2-ylidene (1a). Ostensibly in intermolecular reactions, 5-substituted 2-adamantanylidenes (1) are sterically unbiased. However, inductive effects originating from the pendant group bend the divalent carbon bridge of 1 either toward (ERG's, e.g., -Si(CH3)(3)) or away from (EWG's, e.g., -OH) the gamma-position. Hence, the more exposed side is more susceptible to intermolecular reaction and the other side concomitantly undergoes intramolecular 1,3-CH insertions more readily.

  DOI：

  10.1021/ol0350700

文献信息

• Chung, Wen-Sheng; Liu, Yei-De; Wang, Nae-Jean, Journal of the Chemical Society. Perkin transactions II, 1995, # 3, p. 581 - 586
  作者：Chung, Wen-Sheng、Liu, Yei-De、Wang, Nae-Jean

  DOI：——

  日期：——
• Electrostatic vs Hyperconjugative Effects as Stereoinductive Factors in the Adamantane Ring System
  作者：William Adcock、Jason Cotton、Neil A. Trout

  DOI：10.1021/jo00086a044

  日期：1994.4

  A series of 5-substituted (X) adamant-2-yl derivatives 1 (Y = O and CH2) have been synthesized and their C-13 NMR spectra measured. The carbonyl and ethylenic C-13 substituent chemical shifts (SCS) are shown to be proportional to substituent field effects (sigma(F)). By use of the polar field susceptibility parameter (rho(F)) for the former shifts, polar field parameters (Delta sigma(F) values) have been calculated for a series of p-SC6H4 substituents. II-Facial diastereoselectivities for the reduction (NaBH4) and methylation (MeLi) of para-substituted (S) phenyl derivatives of 1 (Y = O; X = p-SC6H4) and, as well, for the hydrochlorination of similarly substituted alkenes 1 (Y = CH2; X = p-SC6H4) have been determined and correlated successfully against polar field parameters (Delta sigma(F) values). The slopes of these plots (log(10)[Z]/[E] vs Delta sigma(F)) provide polar-field susceptibility parameters (rho(FS)) which have been deployed to calculate appropriate diastereoselectivities of the aforementioned reactions for 5-substituted (X) derivatives of 1 (Y = O and CH2) in general. A comparison of these calculated values with observed diastereoselectivities for a wide range of substituents reveals that direct electrostatic field interactions play a dominant role in governing the phenomena for nucleophilic additions of the ketones 1 (Y = O) and that it is unnecessary to invoke Cieplak's transition-state hyperconjugative model. This appears to be also the case for electrophilic additions to 1 (Y = CH2) not involving final nucleophilic capture of an intermediate cation. However, hyperconjugation clearly impinges significantly on II-facial diastereoselectivity for those reactions mediated by 2-adamantyl cations. New results for methyl-substituted derivatives of 1 (Y = O and CH2, X = CH3) reinforces the sigma-electron-withdrawing character of this substituent with respect to gamma- and delta-interactions in the neutral ground-state and cationic species.
• 2<i>H</i>-Azirines from a Concerted Addition of Alkylcarbenes to Nitrile Groups
  作者：Wolfgang Knoll、Jean-Luc Mieusset、Vladimir B. Arion、Lothar Brecker、Udo H. Brinker

  DOI：10.1021/ol100703r

  日期：2010.5.21

  Photolysis of aziadamantanos in the presence of fumoronitrile (FN) unexpectedly afforded conjugated 2H-azirines resulting from addition of the carbene to the CN triple bond. This represents the first example of a direct azirine formation starting from an alkylcarbene for which a concerted pathway is postulated. The novel outcome if the reaction is favored by the prior formation of a carbene-alkene complex, a type of adduct that only recently has been described.
• Burgess, Kevin; Van Der Donk, Wilfred A.; Jarstfer, Michael B., Journal of the American Chemical Society, 1991, vol. 113, # 16, p. 6139 - 6144
  作者：Burgess, Kevin、Van Der Donk, Wilfred A.、Jarstfer, Michael B.、Ohlmeyer, Michael J.

  DOI：——

  日期：——
• 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.