O-叔-丁基二甲基硅烷基11,12-二去氢视黄醇 | 210700-51-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: O-叔-丁基二甲基硅烷基11,12-二去氢视黄醇
• 中文别名: 邻叔丁基二甲基甲硅烷基11,12-二氢视黄醇
• 英文名称: tert-butyldimethylsilyl (7E,9E,13E)-11,12-didehydroretinyl ether
• 英文别名: ((2E,6E,8E)-3,7-dimethyl-9-(2,6,6-trimethylcyclohex-1-enyl)nona-2,6,8-trien-4-ynyloxy)(tert-butyl)dimethylsilane；O-tert-Butyldimethylsilyl 11,12-Didehydro Retinol；tert-butyl-[(2E,6E,8E)-3,7-dimethyl-9-(2,6,6-trimethylcyclohexen-1-yl)nona-2,6,8-trien-4-ynoxy]-dimethylsilane
• CAS: 210700-51-9
• 化学式: C₂₆H₄₂OSi
• 分子量: 398.704
• InChiKey: FWMKSMNLDOXYCJ-PMCBPKONSA-N

物化性质

• 溶解度：
  可溶于氯仿、二氯甲烷、己烷

计算性质

• 辛醇/水分配系数(LogP)：
  7.99
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  O-叔-丁基二甲基硅烷基11,12-二去氢视黄醇 在 四丁基氟化铵 、 水 、 银 、 铜 、 锌 作用下， 以 四氢呋喃 、 异丙醇 为溶剂， 反应 21.0h， 生成 维生素A
  参考文献：
  名称：

  Efficient Synthesis of 11-cis-Retinoids

  摘要：

  The light sensitivity and unstable nature of 11-cis-retinoids makes them ideal visual chromophores in nature. The synthesis of 11-cis-retinal analogues is of paramount importance in bioorganic studies of rhodopsin, the photoreceptor of the visual transduction pathway, but the instability of 11-cis-retinoids complicates their synthesis and there is no general synthetic route. Common strategies to the cis geometry have failed in the case of 11-cis-retinoids, and most often low yields and complex isomeric mixtures are obtained. Herein we report an efficient, general, and mild preparation of 11-cis-retinoids by semi-hydrogenation of 11-yne-retinoid precursors with Cu/Ag-activated zinc dust.

  DOI：

  10.1002/(sici)1521-3765(19990401)5:4<1172::aid-chem1172>3.0.co;2-q
• 作为产物：
  描述：

  4-(1,4-二甲基-1-乙基)戊基酚 在 copper(l) iodide 、 四(三苯基膦)钯 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 异丙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 O-叔-丁基二甲基硅烷基11,12-二去氢视黄醇
  参考文献：
  名称：

  Accurate Measurements of ¹³C−¹³C J-Couplings in the Rhodopsin Chromophore by Double-Quantum Solid-State NMR Spectroscopy

  摘要：

  A new double-quantum solid-state NMR pulse sequence is presented and used to measure one-bond 13C-13C J-couplings in a set of 13C2-labeled rhodopsin isotopomers. The measured J-couplings reveal a perturbation of the electronic structure at the terminus of the conjugated chain but show no evidence for protein-induced electronic perturbation near the C11-C12 isomerization site. This work establishes NMR methodology for measuring accurate 1JCC values in noncrystalline macromolecules and shows that the measured J-couplings may reveal local electronic perturbations of mechanistic significance.

  DOI：

  10.1021/ja0581604

文献信息

• A Pericyclic Cascade to the Stereocontrolled Synthesis of 9-<i>cis</i>-Retinoids
  作者：Beatriz Iglesias、Alicia Torrado、Angel R. de Lera、Susana López

  DOI：10.1021/jo991757f

  日期：2000.5.1

  trimethylcyclohexenyl substituent at the other terminus. The overall process thus constitutes a stereoselective synthesis of an E,Z,Z-triene fragment from an alkenynol and, in particular, a retinoid with the 7E,9Z,11Z,13E configuration on the conjugated polyenic side chain. Application of this method to the synthesis of retinoids, including labeled analogues, is straightforward.

  据认为，本质上是环周的多米诺反应是在用芳基亚磺酰氯处理链烯醇10时引发的。该过程包括一个σ序的重排的有序序列：可逆的[2,3]-烯丙基亚磺酸盐向烯丙基亚砜的转变，然后是[2,3]-炔丙基亚磺酸盐向烯丙基亚砜的重排，最后是立体分化[1,5]。 -σ氢迁移导致多烯13.标记实验已证明C7至C11氢迁移的发生。据认为，[1,5]-σ氢位移的双非对映选择性是最终多烯13的单一异构体，这是由于亚砜在一个末端的电子效应和庞大的空间效应共同产生的在另一个末端有三甲基环己烯基取代基。因此，整个过程构成了由烯醛醇，特别是在共轭多烯侧链上具有7E，9Z，11Z，13E构型的类维生素A的E，Z，Z-三烯片段的立体选择性合成。这种方法在类维生素A（包括标记类似物）的合成中的应用很简单。
• Syntheses of 13C2-labelled 11Z-retinals
  作者：Neville J. McLean、Axel Gansmuller、Maria Concistre、Lynda J. Brown、Malcom H. Levitt、Richard C.D. Brown

  DOI：10.1016/j.tet.2011.07.092

  日期：2011.10

  To enable solid-state NMR investigations of the rhodopsin chromophore and its photointermediates, a series of 11Z-retinal isotopomers have been synthesised containing pairs of adjacent C-13 labels at C9/C10, C10/C11 or C11/C12, respectively. The C9 labelled carbon atom was introduced through the Heck reaction of a C-13-labelled Weinreb acrylamide derivative, and the label at the C12 position derived from a C-13-containing ethoxy Bestmann-Ohira reagent. The C-13 labels at C10 and C11 were introduced through the reaction of beta-ionone with labelled triethyl phosphonoacetate. (C) 2011 Elsevier Ltd. All rights reserved.
• Stereoselective isomerization of 10-arylsulfenate-11,12-dehydroretinoids to 9-cis-retinoids
  作者：Angel R. de Lera、Alejandro Castro、Alicia Torrado、Susana López

  DOI：10.1016/s0040-4039(98)00810-7

  日期：1998.6

  The C-7-C-12 triene fragment of 9-cis-retinoids 8 was stereoselectively generated by treatment of propargylic alcohol 3 with phenylsulfenyl chloride/triethylamine at -78 degrees C, followed by stereospecific reduction of the resulting vinylsulfoxide (t-BuLi, MeLi, MeOH, -78 degrees C). Thus, 9-cis-retinoic acid 2, the natural ligand of the retinoid X receptor (RXR) was straightforwardly synthesized from 8 in two steps. (C) 1998 Elsevier Science Ltd. All rights reserved.