三甲基甲硅烷基炔丙基膦酸二甲酯 | 228120-29-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 中文名称: 三甲基甲硅烷基炔丙基膦酸二甲酯
• 英文名称: dimethyl (3-trimethylsilyl-2-propynyl)phosphonate
• 英文别名: 3-Dimethoxyphosphorylprop-1-ynyl(trimethyl)silane
• CAS: 228120-29-4
• 化学式: C₈H₁₇O₃PSi
• 分子量: 220.28
• InChiKey: OOMASFPQMMUBTO-UHFFFAOYSA-N

物化性质

• 溶解度：
  可溶于氯仿、可溶于二氯甲烷、乙酸乙酯

计算性质

• 辛醇/水分配系数(LogP)：
  2.35
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  beta-紫罗酮 、 三甲基甲硅烷基炔丙基膦酸二甲酯 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 以99%的产率得到trimethyl((5E)-4-methyl-6-(2,6,6-trimethylcyclohex-1-enyl)hexa-3,5-dien-1-ynyl)silane
  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

文献信息

• Synthetic Studies on Amphidinolide B1
  作者：Amit K. Mandal、John S. Schneekloth,、Kouji Kuramochi、Craig M. Crews

  DOI：10.1021/ol052620g

  日期：2006.2.1

  amphidinolide B1 have been accomplished. The 1,3-isomerization of allylic alcohol 10 was accomplished via rhenium oxo catalysis and has been applied successfully in the synthesis. (-)-MIB-catalyzed asymmetric vinylzinc addition to aldehyde 31 and the regio- and stereoselective epoxidation of unsymmetrical divinyl methanol 32 were key steps.

  [结构：见文字]。两性霉素B1的三个片段2、3和4的合成已经完成。烯丙基醇10的1，3-异构化是通过rh氧羰基催化完成的，并已成功地用于合成中。除醛31外，（-）-MIB催化的不对称乙烯基锌以及不对称二乙烯基甲醇32的区域和立体选择性环氧化是关键步骤。
• Kinetic resolution of racemic allylic alcohols <i>via</i> iridium-catalyzed asymmetric hydrogenation: scope, synthetic applications and insight into the origin of selectivity
  作者：Haibo Wu、Cristiana Margarita、Jira Jongcharoenkamol、Mark D. Nolan、Thishana Singh、Pher G. Andersson

  DOI：10.1039/d0sc05276k

  日期：——

  Asymmetric hydrogenation is one of the most commonly used tools in organic synthesis, whereas, kinetic resolution via asymmetric hydrogenation is less developed. Herein, we describe the first iridium catalyzed kinetic resolution of a wide range of trisubstituted secondary and tertiary allylic alcohols. Large selectivity factors were observed in most cases (s up to 211), providing the unreacted starting

  不对称氢化是有机合成中最常用的工具之一，而通过不对称氢化进行动力学拆分的开发较少。在此，我们描述了各种三取代仲和叔烯丙醇的第一次铱催化动力学拆分。在大多数情况下观察到较大的选择性因子（高达211），从而以良好的收率和高水平的对映体纯度（ee 高达 >99%）提供未反应的起始材料。该方法的实用性在一些生物活性天然产物的对映选择性正式合成中得到了强调，包括 pumiliotoxin A、inthomycin A 和 B。提出了 DFT 研究和关于选择性起源的选择性模型。
• Asymmetric Total Synthesis of Antibiotic Elansolid A
  作者：Liang-Liang Wang、Qi Yu、Wenjing Zhang、Shuai Yang、Lin Peng、Liang Zhang、Xiao-Nian Li、Fabien Gagosz、Andreas Kirschning

  DOI：10.1021/jacs.2c01133

  日期：2022.4.20

  Elansolid A is a structurally complex polyketide macrolactone natural product that exhibits promising antibacterial properties. Its challenging asymmetric total synthesis was achieved by a convergent strategy, in which the tetrahydroindane core of the molecule and an eastern vinyl iodide moiety were combined as the main fragments. The central tetrahydroindane motif was constructed with high stereoselectivity

  Elansolid A 是一种结构复杂的聚酮化合物大环内酯天然产物，具有良好的抗菌性能。其具有挑战性的不对称全合成是通过收敛策略实现的，其中分子的四氢茚满核心和东部碘乙烯部分结合为主要片段。通过仿生分子内 Diels-Alder 环加成，以高立体选择性构建中心四氢茚满基序，一步生成四个立体中心。这一关键步骤的立体控制可以通过在基板上临时引入空间定向碘取代基产生的 1,3-烯丙基应变来实现。完成合成的大环内酯基序的形成是通过两种不同的逆合成断开实现的，即，
• On the Bioactive Conformation of the Rhodopsin Chromophore: Absolute Sense of Twist around the 6-s-cis Bond
  作者：Yukari Fujimoto、Jun Ishihara、Shojiro Maki、Naoko Fujioka、Tao Wang、Takumi Furuta、Nathan Fishkin、Babak Borhan、Nina Berova、Koji Nakanishi

  DOI：10.1002/1521-3765(20011001)7:19<4198::aid-chem4198>3.0.co;2-x

  日期：2001.10.1

  carrying the ring moiety. The GTP-binding assay of pigment Rh-(2a), incorporating retinal analogue 2a, has shown that its activity is 80% that of the native pigment. That is, the overall conformation around the 6-s bond is retained in the steps leading to G-protein activation.

  将视蛋白与合成的6-s锁定类视色素2a和2b一起孵育只会导致由α锁定的2a形成色素，其CD光谱与天然视紫红质（Rh）相似。这表明视紫红质中发色团的6-s键为顺式，且其螺旋度为负。较早的交联研究表明，在batho-Rh到lumi-Rh的转化中发生的11-顺式到全反式光异构化引起了带有环部分的一侧的翻转。结合视网膜类似物2a的色素Rh-（2a）的GTP结合测定表明，其活性是天然色素的80％。即，在导致G蛋白活化的步骤中保留了6-s键周围的整体构象。
• Synthesis of biotinylated retinoids for cross-linking and isolation of retinol binding proteins
  作者：Nasri Nesnas、Robert R Rando、Koji Nakanishi

  DOI：10.1016/s0040-4020(02)00667-1

  日期：2002.8

  The synthesis of (3R)-3-[Boc-Lys(biotinyl)-O]-11-cis-retinol bromoacetate and 3-[Boc-Lys(biotinyl)-0]-all trans-retinol chloroacetate is described. These biotinylated retinoids a-re instrumental in labeling the retinol binding proteins (RBPs) via a nucleophilic displacement of the haloacetate by a residue in the binding site of the protein. The covalently linked biotin will allow for a facile isolation and purification of the protein on a streptavidin column thus rendering the protein ready for a tryptic digest followed by mass spectrometric analysis. The 11-cis retinoid was synthesized via metal reduction of an alkyne intermediate generated from a Homer-Wadsworth-Emmons (HWE) reaction whereas the all-trans was synthesized via two consecutive HWE couplings. (C) 2002 Elsevier Science Ltd. All rights reserved.