trans-1,4-di-tert-butyldimethylsilyloxy-but-2-ene | 162369-35-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: trans-1,4-di-tert-butyldimethylsilyloxy-but-2-ene
• 英文别名: (E)-1,4-bis(tert-butyldimethylsilyloxy)-2-butene；1,4-di-(tert-butyldimethylsilyloxy)but-2-ene；(E)-1,4-Bis{[(tert-butyl)dimethylsilyl]oxy}but-2-ene；2-Butene-1,4-diol, 2TBDMS derivative；tert-butyl-[(E)-4-[tert-butyl(dimethyl)silyl]oxybut-2-enoxy]-dimethylsilane
• CAS: 162369-35-9
• 化学式: C₁₆H₃₆O₂Si₂
• 分子量: 316.632
• InChiKey: CCKLXIOYANFXKC-VAWYXSNFSA-N

物化性质

• 沸点：
  312.2±30.0 °C(Predicted)
• 密度：
  0.854±0.06 g/cm3(Predicted)
• 保留指数：
  1602.7

计算性质

• 辛醇/水分配系数(LogP)：
  5.59
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-1,4-di-tert-butyldimethylsilyloxy-but-2-ene 在 4-二甲氨基吡啶 、 dirhodium tetraacetate 、 硫酸 、 红铝 、 sodium nitrite 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 17.0h， 生成
  参考文献：
  名称：

  Synthesis and Antiviral Activity of Novel Acyclic Nucleosides:  Discovery of a Cyclopropyl Nucleoside with Potent Inhibitory Activity against Herpesviruses

  摘要：

  A series of acyclic nucleosides with two hydroxymethyl groups mimicking the 3'- and 5'-hydroxyl groups of the 2'-deoxyribose moiety were prepared and evaluated for their antiherpetic activity. Among those, 9-[[cis-1',2'-bis(hydroxymethyl)cycloprop-1'yl]methyl]guanine (3) showed extremely potent antiviral activity against herpes simplex virus type-1 (HSV-1) with good selectivity. Both enantiomers of 3 were synthesized stal ting from chiral epichlorohydrins, and only one of the enantiomers with 1'S,2'R-configuration (3a) exhibited strong antiherpetic activity (IC50 of 0.020 mu g/mL against HSV-1 Tomioka vs 0.81 mu g/mL for acyclovir). Enantiomer 3a was also more inhibitory than acyclovir against varicella-zoster virus (VZV) but ineffective against human immunodeficiency virus (HIV). Compound 3a is phosphorylated by HSV-1 thymidine kinase (TK) very efficiently. The relationship between conformation and antiherpetic activity in this series of compounds is discussed.

  DOI：

  10.1021/jm9705869
• 作为产物：
  描述：

  叔丁基二甲基烯丙基硅醚 在 Grubbs catalyst first generation 作用下， 以 苯 为溶剂， 反应 4.17h， 生成 trans-1,4-di-tert-butyldimethylsilyloxy-but-2-ene
  参考文献：
  名称：

  E/Z product distribution in the metathesis of allyl alcohol derivatives with a first generation ruthenium-based catalyst

  摘要：

  Based on experiments with four simple derivatives of allyl alcohol, it has been shown that the product of cross-metathesis as mediated by a 'first generation' ruthenium catalyst increases in its proportion of the E-isomer as the reaction progresses. This increase is due to equilibration, which is also mediated by the ruthenium catalyst. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.05.090

文献信息

• Palladium-catalysed alkene chain-running isomerization
  作者：Andrew L. Kocen、Maurice Brookhart、Olafs Daugulis

  DOI：10.1039/c7cc04953f

  日期：——

  We report a method for palladium-catalysed chain-running isomerization of terminal and internal alkenes. Using an air-stable 2,9-dimethylphenanthroline-palladium catalyst in combination with NaBAr4 promoter, olefins are converted to the most stable double bond isomer at −30 to 20 °C. Silyl enol ethers are readily formed from silylated allylic alcohols. Fluorinated substituents are compatible with the

  我们报告了末端和内部烯烃的钯催化链运行异构化的方法。使用空气稳定的2,9-二甲基菲咯啉-钯催化剂与NaBAr 4助催化剂结合，可在-30至20°C的条件下将烯烃转化为最稳定的双键异构体。甲硅烷基烯醇醚易于由甲硅烷基化的烯丙醇形成。氟化取代基与反应条件相容，从而可以合成氟烯酸酯。可以以克为单位使用低至0.05％的催化剂负载量。
• HIGHLY Z-SELECTIVE OLEFINS METATHESIS
  申请人：Schrock Richard R.

  公开号：US20110077421A1

  公开（公告）日：2011-03-31

  The present invention relates generally to catalysts and processes for the Z-selective formation of internal olefin(s) from terminal olefin(s) via homo-metathesis reactions.

  本发明通常涉及催化剂和过程，用于通过同型交换反应从末端烯烃中Z-选择性地形成内部烯烃。
• The Regio-and Stereo-Chemistry of 1,3-Dipolar Cycloaddition of a Chiral Methylenenitrone to 1,2-Disubstituted Alkenes
  作者：Shaikh A. Ali、Muhammad Z.N. Iman

  DOI：10.3184/030823408x287087

  日期：2008.1

  A study of regio- and stereo-selectivity in the cycloaddition reactions of a series of symmetrical and unsymmetrical 1,2-disubstituted alkenes to the chiral, internally H-bonded N-(2-hydroxy-1-phenyl)methylenenitrone, has been carried out. The regioselectivity observed in the addition reactions is explained in terms of frontier orbital interactions. The alkenes having a hydroxymethyl substituent at the allylic position are found to undergo regio- as well as highly stereo-selective cycloaddition reactions in the presence of anhydrous magnesium bromide.

  研究人员对一系列对称和不对称的 1,2-二取代烯与手性、内部 H 键的 N-(2-羟基-1-苯基)亚甲基腈酮的环加成反应的区域和立体选择性进行了研究。在加成反应中观察到的区域选择性可以用前沿轨道相互作用来解释。研究发现，在无水溴化镁存在下，烯丙基位置上具有羟甲基取代基的烯烃会发生区域和高度立体选择性的环加成反应。
• Asymmetric synthesis of 4-amino-γ-butyrolactones via lithium amide conjugate addition
  作者：Elin Abraham、Jason W.B. Cooke、Stephen G. Davies、Alan Naylor、Rebecca L. Nicholson、Paul. D. Price、Andrew D. Smith

  DOI：10.1016/j.tet.2007.03.026

  日期：2007.6

  undergo competitive conjugate addition and γ-deprotonation, while γ-tert-butyldimethylsilyloxy but-2-enoates undergo exclusive conjugate addition. Treatment of γ-benzyloxy or γ-tert-butyldimethylsilyloxy but-2-enamides with lithium (R)-N-benzyl-N-(α-methylbenzyl)amide furnishes exclusively the γ-benzyloxy- or γ-tert-butyldimethylsilyloxy-β-amino amide products of conjugate addition in high de. The γ

  经高手性锂（R）-N-苄基-N-（α-甲基苄基）酰胺处理后，γ-苄氧基丁-2-烯酸酯竞争性共轭加成和γ-去质子化，而γ-叔丁基二甲基甲硅烷氧基丁-2-烯酸酯进行排他性共轭加成。用锂（R）-N-苄基-N-（α-甲基苄基）酰胺处理γ-苄氧基或γ-叔丁基二甲基甲硅烷氧基丁-2-烯酰胺仅提供γ-苄氧基-或γ-叔丁基二甲基甲硅烷氧基-β-氨基酰胺类高价共轭物加成产物。γ-叔胺共轭加成的-丁基二甲基甲硅烷氧基-β-氨基丁酸产物易于进行O-去甲硅烷基化和伴随的环化反应，以提供4- [ N-苄基-N-（α-甲基苄基）氨基]-γ-丁内酯，可以通过去质子化和烷基化得到相应的反式-3-烷基-4-氨基-γ-丁内酯。或者，烷基化立体选择性γ苄氧基或γ-叔-butyldimethylsilyloxy-β氨基通过烯醇化物的形成和烷基化以下串联丁酸酯和butanamides（经由（Ž） -锂烯醇化物）或逐步（经由（ë）
• The Synthesis of a Novel Epoxycyclohexane from the FungusEutypa lata (Pers: F.) TUL
  作者：Eric Defrancq、John Gordon、Andr� Brodard、Raffaele Tabacchi

  DOI：10.1002/hlca.19920750123

  日期：1992.2.5

  The synthesis of the novel (1′R*,2′S*,3′R*, 4′S*,5′R*)-1-(3′,4′-epxoy-2′, 5′-dihydroxycyclohexyl)-3-methyl-but-2-enone (2), recently isolated from the culture medium of the fungus Eutypa lata, is described.

  小说（1'的合成- [R *，2'小号*，3' - [R *，4'小号*，5' - [R，4'- epxoy-2'，5'-dihydroxycyclohexyl - 1-（3 *）'描述了最近从真菌Eutypa lata的培养基中分离的）-3-甲基-丁-2-烯酮（2）。