tert-butyldiphenyl(4-phenylbutoxy)silane | 88339-99-5

• 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-butyldiphenyl(4-phenylbutoxy)silane
• 英文别名: Silane, (1,1-dimethylethyl)diphenyl(4-phenylbutoxy)-；tert-butyl-diphenyl-(4-phenylbutoxy)silane
• CAS: 88339-99-5
• 化学式: C₂₆H₃₂OSi
• 分子量: 388.625
• InChiKey: CGLNUTCRXOFPPV-UHFFFAOYSA-N

物化性质

• 沸点：
  463.1±28.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.59
• 重原子数：
  28
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 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-butyldiphenyl(4-phenylbutoxy)silane 在 N-羟基邻苯二甲酰亚胺 、 caesium carbonate 作用下， 以 1,2-二氯乙烷 、 乙腈 为溶剂， 反应 48.0h， 生成 ethyl N-[4-[tert-butyl(diphenyl)silyl]oxy-1-phenylbutyl]carbamate
  参考文献：
  名称：

  Radical Amination of C(sp³)–H Bonds Using N-Hydroxyphthalimide and Dialkyl Azodicarboxylate

  摘要：

  A direct conversion of C(sp(3))-H bonds to C(sp3)-N bonds has been achieved by utilizing catalytic N-hydroxyphthalimide (NHPI) and stoichiometric dialkyl azodicarboxylate. NHPI functions as a precursor of the electron-deficient phthalimide N-oxyl radical (PINO) to abstract hydrogens, and dialkyl azodicarboxylate acts as a trapping agent of the resultant carbon radical to generate the hydrazine derivatives. This C-H amination proceeds in a highly chemoselective manner with a wide applicability to functionalize benzylic, propargylic, and aliphatic C-H bonds. Furthermore, the obtained hydrazine compounds were readily converted to the corresponding carbamates or amines. Hence, the present protocol for direct introduction of the nitrogen functionality serves as a powerful tool for efficient construction of nitrogen-substituted natural products and pharmaceuticals.

  DOI：

  10.1021/jo301840e
• 作为产物：
  描述：

  1-苯基-1,4-丁二醇 在 咪唑 、 三乙基硅烷 、 三(五氟苯基)硼烷 、 碳酸氢钠 作用下， 以 二氯甲烷 为溶剂， 反应 16.41h， 生成 tert-butyldiphenyl(4-phenylbutoxy)silane
  参考文献：
  名称：

  通过一系列的甲酰化和B（C6F5）3催化还原反应对2°苄醇进行化学选择性脱氧

  摘要：

  一系列的甲酰化反应和B（C 6 F 5）3催化的Et 3 SiH还原生成的甲酸使得在存在伯（1°）苄基和叔（3°）的情况下仲（2°）苄基的化学选择性脱氧成为可能）非苄醇。这两个步骤都是化学选择性的，其中甲酰化相对于3°有利于1°和2°，而还原相对于1°有利于2°（Ar ＝芳基，Alk ＝烷基）。

  DOI：

  10.1002/ejoc.202100148

文献信息

• Yb(OTf)3/FeCl3 mediated facile conversion of alcohols, ketals and acid sensitive ethers into diphenylmethyl (DPM) ethers
  作者：G.V.M. Sharma、T. Rajendra Prasad、A.K. Mahalingam

  DOI：10.1016/s0040-4039(00)02108-0

  日期：2001.1

  10 mol% Yb(OTf)3 or FeCl3 have been developed as efficient reagents for the conversion of alcohols into diphenylmethyl (DPM) ethers. Similarly, FeCl3 has also been advantageously utilised to successfully convert ketals and acid sensitive ethers into DPM ethers.

  已开发出10 mol％的Yb（OTf）3或FeCl 3作为将醇转化为二苯甲基（DPM）醚的有效试剂。类似地，FeCl 3也已被有利地用于成功地将缩酮和对酸敏感的醚转化为DPM醚。
• Novel reactivities on tert-butyldimethylsilyl and tert-butyldiphenylsilyl ethers; Application to the synthesis of 11-epi-PGF2.ALPHA..
  作者：YASUHIRO TORISAWA、MASAKATSU SHIBASAKI、SHIRO IKEGAMI

  DOI：10.1248/cpb.31.2607

  日期：——

  A facile 1, 5-migration of tert-butyldimethylsilyl and tert-butyldiphenylsilyl groups in the Witting reaction and under other basic conditions was observed during synthetic studies on prostaglandins. A new method for the cleavage of these two silyl protecting groups to the parent alcohol was developed by the combined use of potassium superoxide and crown ether in dimethyl sulfoxide. Utilizing these new reactivities, an efficient synthesis of 11-epi-PGF2α from the well known Corey lactone was successfully achieved.

  在前列腺素的合成研究中，观察到了在Witting反应及其他碱性条件下，叔丁基二甲基硅基和叔丁基二苯基硅基团的容易1,5迁移。通过在二甲基亚砜中联合使用过氧化钾和冠醚，开发了一种新的方法来裂解这两种硅保护基团，生成母酒。利用这些新的反应性，成功实现了从著名的Corey内酯高效合成11-epi-PGF2α。
• Diverse Site-Selective Transformation of Benzylic and Allylic Silyl Ethers via Organocatalytic Oxidation
  作者：Shohei Hamada、Kaori Sakamoto、Eri Miyazaki、Elghareeb E. Elboray、Yusuke Kobayashi、Takumi Furuta

  DOI：10.1021/acscatal.3c01153

  日期：2023.6.16

  the electronic properties of silyl ethers, thus enabling selective oxidation of benzylic and allylic silyl ethers, despite steric factors. A subsequent one-pot reduction accomplishes the formal deprotection to the corresponding benzylic and allylic alcohols. This catalytic system allows the direct oxidative desymmetrization of bis-benzylic and bis-allylic silyl ethers to access synthetically useful

  我们在此报告了硝酰自由基催化剂1a，它识别甲硅烷基醚的电子特性，从而能够选择性氧化苄基和烯丙基甲硅烷基醚，尽管存在空间因素。随后的一锅还原完成了相应苯甲醇和烯丙醇的正式脱保护。该催化系统允许双苄基和双烯丙基甲硅烷基醚直接氧化去对称，以获得合成上有用的单保护共轭醛，其可应用于一锅对映选择性转化。机理研究表明， 1a中的高电子接受性氧铵物质以及三氟乙酸盐形式的苯基碘鎓双(三氟乙酸盐) (PIFA) 在决定选择性的氢化物转移步骤中发挥着关键作用。
• Radical Amination of C(sp³)–H Bonds Using <i>N</i>-Hydroxyphthalimide and Dialkyl Azodicarboxylate
  作者：Yuuki Amaoka、Shin Kamijo、Tamaki Hoshikawa、Masayuki Inoue

  DOI：10.1021/jo301840e

  日期：2012.11.16

  A direct conversion of C(sp(3))-H bonds to C(sp3)-N bonds has been achieved by utilizing catalytic N-hydroxyphthalimide (NHPI) and stoichiometric dialkyl azodicarboxylate. NHPI functions as a precursor of the electron-deficient phthalimide N-oxyl radical (PINO) to abstract hydrogens, and dialkyl azodicarboxylate acts as a trapping agent of the resultant carbon radical to generate the hydrazine derivatives. This C-H amination proceeds in a highly chemoselective manner with a wide applicability to functionalize benzylic, propargylic, and aliphatic C-H bonds. Furthermore, the obtained hydrazine compounds were readily converted to the corresponding carbamates or amines. Hence, the present protocol for direct introduction of the nitrogen functionality serves as a powerful tool for efficient construction of nitrogen-substituted natural products and pharmaceuticals.
• Chemoselective Deoxygenation of 2° Benzylic Alcohols through a Sequence of Formylation and B(C ₆ F ₅ ) ₃ ‐Catalyzed Reduction
  作者：Sven C. Richter、Martin Oestreich

  DOI：10.1002/ejoc.202100148

  日期：2021.4.15

  A sequence of formylation and B(C6F5)3‐catalyzed reduction of the resulting formate with Et3SiH enables the chemoselective deoxygenation of secondary (2°) benzylic in the presence of primary (1°) benzylic and tertiary (3°) non‐benzylic alcohols. Both steps are chemoselective with the formylation favoring 1° and 2° over 3° and the reduction favoring 2° over 1° (Ar=aryl, Alk=alkyl).

  一系列的甲酰化反应和B（C 6 F 5）3催化的Et 3 SiH还原生成的甲酸使得在存在伯（1°）苄基和叔（3°）的情况下仲（2°）苄基的化学选择性脱氧成为可能）非苄醇。这两个步骤都是化学选择性的，其中甲酰化相对于3°有利于1°和2°，而还原相对于1°有利于2°（Ar ＝芳基，Alk ＝烷基）。