((ethylthio)methoxy)triisopropylsilane | 253586-28-6

• 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: ((ethylthio)methoxy)triisopropylsilane
• 英文别名: Ethylsulfanylmethoxy-tri(propan-2-yl)silane
• CAS: 253586-28-6
• 化学式: C₁₂H₂₈OSSi
• 分子量: 248.505
• InChiKey: MUXHANZAKAJFRL-UHFFFAOYSA-N

物化性质

• 沸点：
  253.4±13.0 °C(Predicted)
• 密度：
  0.875±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.89
• 重原子数：
  15
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  34.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ((ethylthio)methoxy)triisopropylsilane 在 磺酰氯 、 二丁基二氯化锡 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 2.33h， 生成 5'-O-(4,4'-dimethoxytrityl)-2'-O-[[(triisopropylsilyl)oxy]methyl]uridine
  参考文献：
  名称：

  具有 2'-O-[(三异丙基甲硅烷基)氧基]甲基(2'-O-tom)-保护的亚磷酰胺的寡核糖核苷酸 (RNA) 的可靠化学合成

  摘要：

  介绍了一种将 2'-O-[(triisopropylsilyl)oxy]methyl (=tom) 基团引入 N-乙酰化、5'-O-二甲氧基三苯甲基化核糖核苷的方法。相应的 2'-O-tom 保护的亚磷酰胺结构单元以纯形式获得，并成功用于 DNA 合成仪上寡核糖核苷酸的常规合成。在 DNA 偶联条件下（1.5 mmol 合成规模的偶联时间为 2.5 分钟）并以 5-(苄硫基)-1H-四唑 (BTT) 作为活化剂。2'-O-tom 保护的亚磷酰胺表现出 av。耦合产率 >99.4%。N-乙酰基和 2'-O-tom 保护基团的组合实现了可靠和完整的两步脱保护，首先使用 EtOH/H2O 中的 MeNH2，然后使用 THF 中的 Bu4NF，而不会同时破坏产物 RNA 序列。[关于 SciFinder (R)]

  DOI：

  10.1002/1522-2675(20011219)84:12<3773::aid-hlca3773>3.0.co;2-e
• 作为产物：
  描述：

  (乙硫基)甲醇 、 三异丙基氯硅烷 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 反应 14.0h， 以85%的产率得到((ethylthio)methoxy)triisopropylsilane
  参考文献：
  名称：

  Fast and Reliable Automated Synthesis of RNA and Partially 2′-O- Protected Precursors (`Caged RNA') Based on Two Novel, Orthogonal 2′-O-Protecting Groups, Preliminary Communication

  摘要：

  Two sets of RNA phosphoramidites. carrying the (fluoride-labile) 2'-O-[(triisopropylsilyl)oxy]methyl (=tom) group and the (photolabile) [(R)-1-(2-nitrophenyl)ethoxy]methyl (=(R)-npeom) group, were prepared (see 1-4 and 5-8, resp.). The two protecting groups were completely orthogonal to each other. Three ribozyme-substrate constructs, protected each by a (R)-npeom group, were synthesized; on photolysis, efficient cleavage of this remaining protecting group occurred (Scheme 3). It could be demonstrated that the presence of one (R)-npeom group within a RNA strand has only a minor influence on the pairing properties of corresponding duplexes.

  DOI：

  10.1002/(sici)1522-2675(19991006)82:10<1753::aid-hlca1753>3.0.co;2-y

文献信息

• A new method for formacetal linkage formation: protection of alcohols, phenols and carboxylic acids
  作者：Daisuke Sawada、Yukishige Ito

  DOI：10.1016/s0040-4039(01)00212-x

  日期：2001.3

  A new formacetal linkage (ROCH2OR′) forming reaction was developed, which exploited a combination of sulfide (R′OCH2SR″) and CuBr2-Bu4NBr. This reaction proceeded to give high yields under neutral conditions and was applied to the protection of alcohols, phenols and carboxylic acids by several types of α-oxymethyl groups.

  利用硫化物（R'OCH 2 SR”）和CuBr 2 -Bu 4 NBr的组合，开发了一种新的甲醛缩醛键（ROCH 2 OR'）形成反应。该反应在中性条件下进行以得到高产率，并通过几种类型的α-氧甲基被用于保护醇，酚和羧酸。
• Total Synthesis of Leiodermatolide A via Transfer Hydrogenative Allylation, Crotylation, and Propargylation: Polyketide Construction beyond Discrete Allyl- or Allenylmetal Reagents
  作者：Yuk-Ming Siu、James Roane、Michael J. Krische

  DOI：10.1021/jacs.1c06062

  日期：2021.7.21

  The total synthesis of leiodermatolide A was accomplished in 13 steps (LLS). Transfer hydrogenative variants of three carbonyl additions that traditionally rely on premetalated reagents (allylation, crotylation, and propargylation) are deployed together in one total synthesis.

  leiodermatolide A 的全合成分 13 个步骤 (LLS) 完成。传统上依赖于预金属化试剂（烯丙基化、巴豆酰化和炔丙基化）的三种羰基加成的转移氢化变体在一个全合成中一起部署。
• Synthesis of the C(1)–C(13) Fragment of Leiodermatolide via Hydrogen-Mediated C–C Bond Formation
  作者：James Roane、Julian Wippich、Stephen D. Ramgren、Michael J. Krische

  DOI：10.1021/acs.orglett.7b03351

  日期：2017.12.15

  coupling of acetylene with a Roche-type aldehyde is used to construct C(7)–C(13). A 2-propanol-mediated reductive coupling of allyl acetate with (E)-2-methylbut-2-enal at a low loading of iridium (1 mol %) is used to construct C(1)–C(6), which is converted to an allylsilane using Oestereich’s copper-catalyzed allylic substitution of Si–Zn reagents. The union of the C(1)–C(6) and C(7)–C(13) fragments

  抗有丝分裂海洋大环内酯 leiodermatolide 的 C(1)–C(13) 片段通过氢化和转移氢化还原 C–C 偶联分七个步骤制备。乙炔与罗氏醛的氢介导还原偶联用于构建 C(7)–C(13)。在低铱负载量 (1 mol%) 下，乙酸烯丙酯与 ( E )-2-甲基丁-2-烯醛通过 2-丙醇介导的还原偶联构建 C(1)–C(6)，即使用 Oestereich 的铜催化的 Si-Zn 烯丙基取代试剂将其转化为烯丙基硅烷。 C(1)–C(6) 和 C(7)–C(13) 片段的结合是通过立体选择性 Sakurai 烯丙基化实现的。
• Reliable Chemical Synthesis of Oligoribonucleotides (RNA) with 2′-O-[(Triisopropylsilyl)oxy]methyl(2′-O-tom)-Protected Phosphoramidites
  作者：Stefan Pitsch、Patrick A. Weiss、Luzi Jenny、Alfred Stutz、Xiaolin Wu

  DOI：10.1002/1522-2675(20011219)84:12<3773::aid-hlca3773>3.0.co;2-e

  日期：2001.12.19

  A method for the introduction of the 2'-O-[(triisopropylsilyl)oxy]methyl (=tom) group into N-acetylated, 5'-O-dimethoxytritylated ribonucleosides is presented. The corresponding 2'-O-tom-protected phosphoramidite building blocks were obtained in pure form and were successfully employed for the routine synthesis of oligoribonucleotides on DNA synthesizers. Under DNA coupling conditions (2.5 min coupling

  介绍了一种将 2'-O-[(triisopropylsilyl)oxy]methyl (=tom) 基团引入 N-乙酰化、5'-O-二甲氧基三苯甲基化核糖核苷的方法。相应的 2'-O-tom 保护的亚磷酰胺结构单元以纯形式获得，并成功用于 DNA 合成仪上寡核糖核苷酸的常规合成。在 DNA 偶联条件下（1.5 mmol 合成规模的偶联时间为 2.5 分钟）并以 5-(苄硫基)-1H-四唑 (BTT) 作为活化剂。2'-O-tom 保护的亚磷酰胺表现出 av。耦合产率 >99.4%。N-乙酰基和 2'-O-tom 保护基团的组合实现了可靠和完整的两步脱保护，首先使用 EtOH/H2O 中的 MeNH2，然后使用 THF 中的 Bu4NF，而不会同时破坏产物 RNA 序列。[关于 SciFinder (R)]
• Fast and Reliable Automated Synthesis of RNA and Partially 2′-O- Protected Precursors (`Caged RNA') Based on Two Novel, Orthogonal 2′-O-Protecting Groups, Preliminary Communication
  作者：Stefan Pitsch、Patrick A. Weiss、Xiaolin Wu、Damian Ackermann、Thomas Honegger

  DOI：10.1002/(sici)1522-2675(19991006)82:10<1753::aid-hlca1753>3.0.co;2-y

  日期：1999.10.6

  Two sets of RNA phosphoramidites. carrying the (fluoride-labile) 2'-O-[(triisopropylsilyl)oxy]methyl (=tom) group and the (photolabile) [(R)-1-(2-nitrophenyl)ethoxy]methyl (=(R)-npeom) group, were prepared (see 1-4 and 5-8, resp.). The two protecting groups were completely orthogonal to each other. Three ribozyme-substrate constructs, protected each by a (R)-npeom group, were synthesized; on photolysis, efficient cleavage of this remaining protecting group occurred (Scheme 3). It could be demonstrated that the presence of one (R)-npeom group within a RNA strand has only a minor influence on the pairing properties of corresponding duplexes.