tert-butyl(cyclohex-3-en-1-ylmethoxy)dimethylsilane | 290355-85-0

• 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: tert-butyl(cyclohex-3-en-1-ylmethoxy)dimethylsilane
• 英文别名: 1,2,3,6-Tetrahydrobenzylalcohol, tert-butyldimethylsilyl ether；tert-butyl-(cyclohex-3-en-1-ylmethoxy)-dimethylsilane
• CAS: 290355-85-0
• 化学式: C₁₃H₂₆OSi
• 分子量: 226.434
• InChiKey: YCUWDNFNLAVMLA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.36
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 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：

  tert-butyl(cyclohex-3-en-1-ylmethoxy)dimethylsilane 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以92%的产率得到(tert-butyl)(cyclohexylmethoxy)dimethylsilane
  参考文献：
  名称：

  The undesirable lability of tert-butyldimethylsilyl ethers under Pd/C-catalyzed hydrogenation conditions and solution of the problem by using a Pd/C(en) catalyst

  摘要：

  While the frequent and unexpected loss of the TBDMS protective group of a variety of hydroxylic functions was demonstrated under neutral and mild hydrogenation conditions using 10% Pd/C, the undesirable problem was perfectly overcome by using a 10% Pd/C-ethylenediamine complex catalyst. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)00935-7
• 作为产物：
  描述：

  3-环己烯-1-甲醇 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以95%的产率得到tert-butyl(cyclohex-3-en-1-ylmethoxy)dimethylsilane
  参考文献：
  名称：

  基于马来酰亚胺的二烯无金属连接：一项比较研究。

  摘要：

  简短的文献调查表明，无金属的连接（例如，基于马来酰亚胺的环加成反应和富电子的（杂）二烯）是组装（生物）分子系统的广泛工具，并应用于生物技术，材料科学，聚合物和生物化学领域。有机化学。尽管日常使用它们，但只能获得有关其动力学以及相应产品在生理条件下的稳定性的分散数据。这些关键参数对于确保快速有效地制备稳定的化合物至关重要。本文报道了有关化学选择性连接中使用的不同类别二烯的系统研究，包括其可达性和稳定性，以及比较动力学实验和产物稳定性测定。

  DOI：

  10.1039/d0ob00403k

文献信息

• Catalytic Cleavage of C(<i>sp</i>²)–C(<i>sp</i>²) Bonds with Rh-Carbynoids
  作者：Zhaofeng Wang、Liyin Jiang、Pau Sarró、Marcos G. Suero

  DOI：10.1021/jacs.9b08632

  日期：2019.10.2

  We report a catalytic strategy that generates rhodium-carbynoids by selective diazo activation of designed carbyne sources. We found that rhodium-carbynoid species provoke C(sp2)-C(sp2) bond scission in alkenes by inserting a monovalent carbon unit between both sp2-hybridized carbons. This skeletal remodeling process access synthetically useful allyl cation intermediates that conduct to valuable allylic

  我们报告了一种催化策略，该策略通过对设计的碳炔源进行选择性重氮活化来生成铑-carbynoids。我们发现，通过在两个 sp2 杂化碳之间插入一价碳单元，铑-carbynoid 物种会引起烯烃中的 C(sp2)-C(sp2) 键断裂。这种骨架重塑过程获得了合成有用的烯丙基阳离子中间体，这些中间体在亲核试剂攻击时转化为有价值的烯丙基结构单元。我们的结果依赖于能够按照 Woodward-Hoffmann-DePuy 规则进行电环开环的环丙基-I(III) 中间体的形成。
• A mild and chemoselective method for the deprotection of tert-butyldimethylsilyl (TBDMS) ethers using iron(III) tosylate as a catalyst
  作者：Jason M. Bothwell、Veronica V. Angeles、James P. Carolan、Margaret E. Olson、Ram S. Mohan

  DOI：10.1016/j.tetlet.2009.12.076

  日期：2010.2

  TBDMS ethers utilizes stoichiometric amounts of tetrabutylammonium fluoride, n-Bu4N+F− (TBAF), which is highly corrosive and toxic. We have developed a mild and chemoselective method for the deprotection of TBDMS, TES, and TIPS ethers using iron(III) tosylate as a catalyst. Phenolic TBDMS ethers, TBDPS ethers and the BOC group are not affected under these conditions. Iron(III) tosylate is an inexpensive

  为TBDMS醚脱保护的最常见的方法是利用化学计量的量的四丁基氟化铵，Ñ -Bu 4 Ñ + ˚F -（TBAF），这是高度腐蚀性和毒性。我们已经开发了一种温和的化学选择性方法，可使用甲苯磺酸铁（III）作为催化剂对TBDMS，TES和TIPS醚进行脱保护。在这些条件下，不影响酚类TBDMS醚，TBDPS醚和BOC基团。甲苯磺酸铁（III）是一种便宜的，市售的，无腐蚀性的试剂。
• Oligonucleotide conjugation to a cell-penetrating (TAT) peptide by Diels–Alder cycloaddition
  作者：Victoria Steven、Duncan Graham

  DOI：10.1039/b807843b

  日期：——

  Modifed oligonucleotides are routinely employed as analytical probes for use in diagnostics, e.g. in the examination of specific RNA sequences for infectious diseases, however, a major limiting factor in oligonucleotide-based diagnostics is poor cellular uptake of naked oligonucleotides. This problem can be overcome by covalent attachment of a so-called ‘cell-penetrating peptide’ to form an oligonucleotide peptide conjugate. Stepwise solid phase synthesis of such a conjugate is difficult and expensive due to the conflicting chemistries of oligonucleotides and peptides. A simple approach to overcome this is post-synthetic conjugation. Diels–Alder cycloaddition is an attractive methodology for oligonucleotide peptide conjugation; the reaction is fast, chemoselective and the reaction rate is greatly enhanced in aqueous media – ideal conditions for biological moieties. An oligodeoxyribonucleotide sequence has been derivatised with a series of dienes at the 5′-terminus, using a series of unique dienyl-modified phosphoramidites, and investigation into the effect of diene type on the efficiency of conjugation, using Diels–Alder cycloaddition with a maleimido-derivatised cell-penetrating (TAT) peptide, has been performed. This led to the observation that the optimal diene for conjugation was cyclohexadiene, allowing conjugation of oligodeoxyribonucleotides to a cell-penetrating peptide by Diels–Alder cycloaddition for the first time.

  经过修饰的寡核苷酸通常被用作诊断分析探针，例如用于检测传染性疾病的特定RNA序列。然而，寡核苷酸诊断的一个主要限制因素是裸寡核苷酸的细胞吸收率低。通过共价连接所谓的 "细胞穿透肽 "来形成寡核苷酸肽共轭物，可以克服这一问题。由于寡核苷酸和肽的化学性质相互冲突，逐步固相合成这种共轭物既困难又昂贵。克服这一问题的简单方法是合成后共轭。DielsâAlder 环加成法是寡核苷酸与肽共轭的一种有吸引力的方法；该反应速度快、化学选择性好，而且在水介质中反应速率大大提高，是生物分子的理想反应条件。利用一系列独特的二烯基修饰的磷酰胺，在寡脱氧核苷酸序列的 5²-末端用一系列二烯进行了衍生，并利用 DielsâAlder 环加成法与马来酰亚胺衍生化的细胞穿透（TAT）肽进行了二烯类型对共轭效率影响的研究。结果发现，最适合共轭的二烯是环己二烯，从而首次实现了通过 DielsâAlder 环加成法将寡脱氧核苷酸与细胞穿透肽共轭。
• Tailoring chemoenzymatic oxidation <i>via in situ</i> peracids
  作者：Rebecca N. Re、Johanna C. Proessdorf、James J. La Clair、Maeva Subileau、Michael D. Burkart

  DOI：10.1039/c9ob01814j

  日期：——

  often suffers from the challenging handling of peracids and thus requires in situ preparation. Here, we describe a two-phase enzymatic system that allows the effective generation of peracids and directly translate their activity to the epoxidation of olefins. We demonstrate the approach by application to lipid and olefin epoxidation as well as sulfide oxidation. These methods offer useful applications to

  环氧化化学常常面临过酸处理的挑战性，因此需要原位制备。在这里，我们描述了一种两相酶系统，该系统可以有效生成过酸并将其活性直接转化为烯烃的环氧化。我们通过应用于脂质和烯烃环氧化以及硫化物氧化来演示该方法。这些方法为合成修饰和可扩展的绿色工艺提供了有用的应用。
• Method for immobilizing oligonucleotides employing the cycloaddition bioconjugation method
  申请人：——

  公开号：US20030215801A1

  公开（公告）日：2003-11-20

  This invention discloses a novel method for immobilizing molecules to a support. Specifically, this invention discloses a method of immobilizing derivatized biomolecules, such as oligonucleotides, using cycloaddition reactions, such as the Diels-Alder reaction. Included in this invention are the novel immobilized biomolecules that can be prepared according to the method of this invention.

  本发明披露了一种新颖的分子固定到支持材料的方法。具体来说，本发明披露了一种使用环加成反应，例如Diels-Alder反应，固定衍生生物分子（如寡核苷酸）的方法。本发明还包括可以根据本发明方法制备的新型固定生物分子。