2'-Deoxy-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)adenosine | 84828-84-2

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘌呤核苷
• 英文名称: 2'-Deoxy-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)adenosine
• 英文别名: 3',5'-O-[(tetraisopropyl)disiloxane-1,3-diyl]-2'-deoxyadenosine；2'-deoxy-3',5'-O-(tetraisopropyldisiloxane-1,3-diyl)adenosine；3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2'-deoxyadenosine；9-[(6aR,8R,9aS)-2,2,4,4-tetra(propan-2-yl)-6a,8,9,9a-tetrahydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-8-yl]purin-6-amine
• CAS: 84828-84-2
• 化学式: C₂₂H₃₉N₅O₄Si₂
• 分子量: 493.754
• InChiKey: IXPBQYBJOKVCEF-IPMKNSEASA-N

物化性质

• 沸点：
  544.1±60.0 °C(Predicted)
• 密度：
  1.26±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.65
• 重原子数：
  33
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  107
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2'-Deoxy-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)adenosine 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 生成 2'-脱氧腺苷
  参考文献：
  名称：

  Radical deoxygenation and dehalogenation of nucleoside derivatives with hypophosphorous acid and dialkyl phosphites

  摘要：

  Hypophosphorous acid and dialkyl phosphites are effective radical reducing agents for D-thiocarbonyl groups or halides at the sugar part of nucleoside derivatives and give the corresponding hydrocarbons in high yield. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01617-3
• 作为产物：
  描述：

  腺苷 在 吡啶 、 4-二甲氨基吡啶 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 11.0h， 生成 2'-Deoxy-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)adenosine
  参考文献：
  名称：

  Smooth and efficient deoxygenation of secondary alcohols. A general procedure for the conversion of ribonucleosides to 2'-deoxynucleosides

  摘要：

  DOI：

  10.1021/ja00394a033

文献信息

• SENSITIVE OLIGONUCLEOTIDE SYNTHESIS USING SULFUR-BASED FUNCTIONS AS PROTECTING GROUPS AND LINKERS
  申请人：Fang Shiyue

  公开号：US20210032281A1

  公开（公告）日：2021-02-04

  Embodiments for the synthesis of sensitive oligonucleotides as well as insensitive oligonucleotides are provided. Sulfur-based groups are used for the protection of exo-amino groups of nucleobases, phosphate groups and 2′-OH groups, and as cleavable linker for linking oligonucleotides to a support. Oligonucleotide syntheses are achieved under typical conditions using phosphoramidite chemistry with important modifications. To prevent replacing sulfur-based protecting groups by acyl groups via cap-exchange, special capping agents are used. To retain hydrophobic tag to assist RP HPLC purification, special phosphoramidites are used in the last synthetic cycle. With the sulfur-based groups for protection and linking, oligonucleotide deprotection and cleavage are achieved via oxidation followed by beta-elimination under mild conditions. Therefore, besides for insensitive oligonucleotide synthesis, the embodiments of the invention are capable for the synthesis of oligonucleotide analogs containing sensitive functional groups that cannot survive the harsh conditions used in prior art oligonucleotide synthesis technologies.

  本发明提供了用于合成敏感寡核苷酸和不敏感寡核苷酸的实施方案。使用基于硫的基团来保护核苷酸碱基的exo-氨基团、磷酸基团和2′-OH基团，并且作为可裂解的连接剂将寡核苷酸连接到支持物上。寡核苷酸的合成是在典型条件下使用磷酰亚胺化学进行的，并进行了重要的修改。为了防止通过帽交换将基于硫的保护基团替换为酰基，使用了特殊的封端剂。为了保留亲脂性标签以协助反相高效液相色谱（RP HPLC）纯化，在最后的合成周期中使用了特殊的磷酰亚胺。使用基于硫的基团进行保护和连接，寡核苷酸的脱保护和裂解是通过氧化随后在温和条件下进行beta-消除实现的。因此，除了用于不敏感寡核苷酸的合成外，本发明的实施方案还能够合成包含在先前的寡核苷酸合成技术中使用的严酷条件下无法存活的敏感功能团的寡核苷酸类似物。
• Electrophilic oligodeoxynucleotide synthesis using dM-Dmoc for amino protection
  作者：Shahien Shahsavari、Dhananjani N A M Eriyagama、Bhaskar Halami、Vagarshak Begoyan、Marina Tanasova、Jinsen Chen、Shiyue Fang

  DOI：10.3762/bjoc.15.108

  日期：——

  Solid-phase synthesis of electrophilic oligodeoxynucleotides (ODNs) was achieved using dimethyl-Dmoc (dM-Dmoc) as amino protecting group. Due to the high steric hindrance of the 2-(propan-2-ylidene)-1,3-dithiane side product from deprotection, the use of excess nucleophilic scavengers such as aniline to prevent Michael addition of the side product to the deprotected ODN during ODN cleavage and deprotection

  使用二甲基-Dmoc（dM-Dmoc）作为氨基保护基，实现了亲电性寡聚脱氧核苷酸（ODN）的固相合成。由于2-（丙烷-2-亚烷基）-1,3-二硫杂环丁烷副产物脱保护的高度位阻，因此在使用期间使用过量的亲核清除剂（例如苯胺）可防止将副产物迈克尔加成到脱保护的ODN中不再需要ODN裂解和脱保护。五个ODN（包括三个修饰的ODN）的合成和表征证明了改进的技术。改性的ODN含有亲电子基团乙酯，α-氯酰胺和硫代酯。使用该技术，可以将敏感组安装在ODN序列内的任何位置，而无需使用任何特定于序列或功能的条件和程序。
• Reactivity of Nucleosides with a Hydroxyl Radical in Non-aqueous Medium
  作者：Gemma M. Rodríguez-Muñiz、M. Luisa Marin、Virginie Lhiaubet-Vallet、Miguel A. Miranda

  DOI：10.1002/chem.201201090

  日期：2012.6.25

  DNA damage: The reactivity of HO. with silylated 2′‐deoxyribonucleosides was investigated in acetonitrile by means of a time‐resolved technique. The obtained rate constants were in general slightly lower than those reported for the natural nucleosides in water. Analysis of the reaction mixture by UPLC‐MS revealed that HO. attack occurred at the nucleobase (see scheme).

  DNA损伤：HO的反应性。通过时间分辨技术研究了乙腈中甲硅烷基化的2'-脱氧核糖核苷的含量。所获得的速率常数通常略低于在水中报道的天然核苷的速率常数。通过UPLC-MS分析反应混合物，发现HO 。攻击发生在核碱基上（见方案）。
• Radical-based deoxygenation of aliphatic alcohols via thioxocarbamate derivatives
  作者：Makoto Oba、Kozaburo Nishiyama

  DOI：10.1016/s0040-4020(01)81751-8

  日期：1994.8

  N-Phenylthioxocarbamates, obtained from the reaction of alcohols with phenyl isothiocyanate in the presence of NaH, were reduced with various silanes such as triethylsilane, triphenylsilane, and tris(trimethylsilyl)silane, as well as tributylstannane under radical conditions to give deoxygenated products of the corresponding alcohols in excellent yields. The reaction was applicable to not only simple aliphatic

  在NaH存在下，将醇与异硫氰酸苯酯反应制得的N-苯基硫代氨基甲酸酯，在自由基条件下，用各种硅烷（如三乙基硅烷，三苯基硅烷和三（三甲基甲硅烷基）硅烷）和三丁基锡烷还原，得到苯甲酸酯的脱氧产物。相应的醇，收率很高。该反应不仅适用于简单的脂族醇，而且适用于糖和核苷。在相似条件下，还研究了使用氘代硅烷和氘代锡烷烷的区域选择性和立体选择性氘代。
• Synthetic utility of 1,1,2,2-tetraaryldisilanes: radical reduction of alkyl phenyl chalcogenides
  作者：Osamu Yamazaki、Hideo Togo、Masataka Yokoyama

  DOI：10.1039/a905937g

  日期：——

  Reactivity of tetraaryldisilanes as radical reducing agents of alkyl phenyl chalcogenides initiated by Et3B or AIBN was studied. Here, the reactivity of alkyl sulfide was poor; however, various alkyl phenyl selenides and tellurides were reduced to the corresponding hydrocarbons in good yields with 1,1,2,2-tetraphenyldisilane.

  研究了由Et 3 B或AIBN引发的四芳基乙硅烷作为烷基苯基硫族化物自由基还原剂的反应性。在此，烷基硫化物的反应性差。但是，用1,1,2,2-四苯基乙硅烷可将各种烷基苯基硒化物和碲化物以良好的收率还原为相应的烃类。