tert-butyl(cyclohexa-2,4-dien-1-ylmethoxy)dimethylsilane | 359867-66-6

• 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(cyclohexa-2,4-dien-1-ylmethoxy)dimethylsilane
• 英文别名: 5-(tert-butyldimethylsilyloxymethyl)cyclohexa-1,3-diene；tert-butyl(cyclohexa-2,4-dienylmethoxy)dimethylsilane
• CAS: 359867-66-6
• 化学式: C₁₃H₂₄OSi
• 分子量: 224.418
• InChiKey: ZTMNQYHQJBKIHN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.14
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  tert-butyl(cyclohexa-2,4-dien-1-ylmethoxy)dimethylsilane 在 吡啶 、 Dowex H(+) 、 potassium carbonate 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 {(R)-5-[Bis-(4-methoxy-phenyl)-phenyl-methoxy]-3-[(2-cyano-ethoxy)-diisopropylamino-phosphanyloxy]-pentyl}-carbamic acid cyclohexa-2,4-dienylmethyl ester
  参考文献：
  名称：

  COVALENT MODIFICATION AND SURFACE IMMOBILIZATION OF NUCLEIC ACIDS VIA THE DIELS-ALDER BIOCONJUGATION METHOD

  摘要：

  The importance of chemically modified and surface immobilized nucleic acids has inspired the development of a wide variety of complementary techniques for covalent oligonucleotide preparation and immobilization. We are developing technology based on the use of a Diels-Alder reaction for accomplishing the covalent modification of oligonucleotides. Reported herein is preliminary progress toward the establishment of robust reagents for introducing the reactive functionality, as well as studies employing the BIACORE system to demonstrate surface immobilization by the method.

  DOI：

  10.1081/ncn-100002332
• 作为产物：
  描述：

  (+/-)-cis/trans-2-{[(tert-butyl)(dimethyl)silyloxy]methyl}cyclohexanol 在 正丁基锂 、 cerium(III) chloride heptahydrate 、 氧气 、 palladium diacetate 、 silica gel 、 2,4-二硝基苯硫氯 、 三乙胺 、 N,N-二异丙基乙胺 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 二甲基亚砜 、 1,2-二氯乙烷 为溶剂， -78.0~83.0 ℃ 、101.33 kPa 条件下， 反应 32.0h， 生成 tert-butyl(cyclohexa-2,4-dien-1-ylmethoxy)dimethylsilane
  参考文献：
  名称：

  A Boron-Based Synthesis of the Natural Product (+)-trans-Dihydrolycoricidine

  摘要：

  DOI：

  10.1002/anie.201007135

文献信息

• Maleimide-based metal-free ligation with dienes: a comparative study
  作者：Alexis Lossouarn、Kévin Renault、Laetitia Bailly、Axel Frisby、Patricia Le Nahenec-Martel、Pierre-Yves Renard、Cyrille Sabot

  DOI：10.1039/d0ob00403k

  日期：——

  maleimide-based cycloaddition with electron-rich (hetero)dienes is a widespread tool for the assembly of (bio)molecular systems with applications in biotechnology, materials science, polymers and bio-organic chemistry. Despite their everyday use, only scattered data about their kinetics as well as the stabilities of corresponding products under physiological conditions, are accessible. These key parameters are yet

  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。
• 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。
• Diels−Alder Bioconjugation of Diene-Modified Oligonucleotides
  作者：Kenneth W. Hill、Jon Taunton-Rigby、Jeffrey D. Carter、Eric Kropp、Kurt Vagle、Wolfgang Pieken、Danny P. C. McGee、Gregory M. Husar、Michael Leuck、Dominic J. Anziano、David P. Sebesta

  DOI：10.1021/jo0100190

  日期：2001.8.1

  In an effort to offer complementary technology for covalent biomolecule modification (bioconjugation), we have developed a method that exploits the aqueous acceleration of Diels-Alder reactions for this purpose. Three different diene phosphoramidite reagents have been synthesized that enable diene modification of synthetic oligonucleotides prepared by the phosphoramidite method. Clean and efficient Diels-Alder cycloaddition of these diene oligonucleotides with maleimide dieneophiles was carried out, and the labeled oligonucleotide bioconjugates were characterized by HPLC and electrospray mass spectrometry. Dieneophile stoichiometry, temperature, and pH are all parameters that were shown to influence the efficiency of the process.