(2-Triisopropylsilanyl-furan-3-yl)-methanol | 117657-97-3

• 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: (2-Triisopropylsilanyl-furan-3-yl)-methanol
• 英文别名: [2-Tri(propan-2-yl)silylfuran-3-yl]methanol
• CAS: 117657-97-3
• 化学式: C₁₄H₂₆O₂Si
• 分子量: 254.445
• InChiKey: BVYGLQZVQIMOBT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.66
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  33.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2-Triisopropylsilanyl-furan-3-yl)-methanol 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以89%的产率得到(furan-3-ylmethoxy)triisopropylsilane
  参考文献：
  名称：

  The 1,4 C→O silyl migrations of various furan and thiophene systems

  摘要：

  DOI：

  10.1016/s0040-4039(00)99574-1
• 作为产物：
  描述：

  (furan-3-ylmethoxy)triisopropylsilane 在 正丁基锂 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 正己烷 为溶剂， 以86%的产率得到(2-Triisopropylsilanyl-furan-3-yl)-methanol
  参考文献：
  名称：

  Regioselective Preparation of 2,4-, 3,4-, and 2,3,4-Substituted Furan Rings. 1. [1,4] O → C and [1,4] C → O Silyl Migrations of Silyl Ethers and Esters Attached to Furan and Thiophene Rings

  摘要：

  [1,4] O --> C and [1,4] C --> O rearrangements are described for a variety of furans and thiophenes. Treatment of 3-((silyloxy)methyl)furans and -thiophenes with n-BuLi in HMPA provided 2-silylated-3-(hydroxymethyl)furans and -thiophenes in good to excellent yields. The reaction was shown by crossover studies to proceed via an intramolecular [1,4] O --> C silyl migration. Silyl esters of 3-furoic acids also underwent an intramolecular [1,4] O --> C silyl migration to provide 2-silylated-3-furoic acids in moderate to good yield when treated with a mixture of LDA and HMPA. Finally, the above silyl migrations were shown to be reversible. Treatment of 2-silylated-3-(hydroxymethyl)furans and -thiophenes with NaH in DMF provided 3-((silyloxy)methyl)furans and -thiophenes in excellent yields via a [1,4] C --> O silyl migration. The [1,4] C --> O silyl migration was also shown to be an intramolecular process by a crossover study.

  DOI：

  10.1021/jo971097j

文献信息

• The regiospecific formation and reactions of 4-lithio-2-(t-butyldimethylsilyl)- 3-(hydroxymethyl)furan: An approach to 3,4-disubstituted furans.
  作者：Edward J. Bures、Brian A. Keay

  DOI：10.1016/s0040-4039(00)80267-1

  日期：1988.1

  4-Lithio-2-(t-butyldimethylsilyl)-3-(hydroxymethyl)furan, generated by treating 2-(t-butyldimethylsilyl)-3-(hydroxymethyl)furan with 2.2 equivalents of n-butyllithium (DME/0°C/15 min), is trapped by a variety of electrophiles to produce, after desilylation, 3,4-disubstituted furans in good to moderate yields.

  通过用2.2当量的正丁基锂（DME / 0°C /在15分钟内）被各种亲电试剂捕获，去甲硅烷基化后可产生3,4-二取代的呋喃，产率中等至中等。
• Regioselective Preparation of 2,4-, 3,4-, and 2,3,4-Substituted Furan Rings. 2.¹ Regioselective Lithiation of 2-Silylated-3-substituted Furan Rings
  作者：Edward Bures、James A. Nieman、Shuyuan Yu、Patrick G. Spinazzé、Jean-Louis J. Bontront、Ian R. Hunt、Arvi Rauk、Brian A. Keay

  DOI：10.1021/jo971098b

  日期：1997.12.1

  A new method for the preparation of 3,4- and 2,5-disubstituted furan rings is described. A variety of 2-silylated-3-(hydroxymethyl)furans and 2-silylated-3-furoic acids lithiate exclusively at C-4 when treated with 2.2 equivs of BuLi. The resulting dianions were quenched with a variety of electrophiles to provide 2-silylated-3-(hydroxymethyl)-substituted furans and 2-silylated-4-substituted 3-furoic acids in good to excellent yields. Removal of the silyl group (n-Bu4NF) provided a variety of 4-substituted-3-(hydroxymethyl)furans and methyl 4-substituted-3-furoates, respectively. The latter esters were prepared due to difficulties encountered in isolating 4-substituted-3-furoic acids. The site of lithiation was altered by protecting the 3-hydroxyl group with a triethylsilane. Lithiation of 2-silylated-3-(((triethylsilyl)oxy)methyl)furan with 1.2 equivs of BuLi followed by the addition of electrophiles provided 2-silylated-3-(((triethylsilyl)oxy)methyl)-5-substituted furan rings. Subsequent removal of both silyl groups provided 2,4-disubstituted furan rings in moderate to good yields. A rationale is provided to explain why protection of the hydroxyl group at C-3 leads to a change in lithiation from the C-4 to the C-5 position of the furan ring. In addition, an explanation for the observed effect of adding HMPA or LiCl to the solution during the lithiation of 2-(tert-butyldimethylsilyl)-3-(hydroxymethyl)furan is provided.
• The 1,4 O→C silyl migrations of various 3-[(trialkylsilyl)oxymethyl]-furans and -thiophenes
  作者：Edward J. Bures、Brian A. Keay

  DOI：10.1016/s0040-4039(00)96838-2

  日期：1987.1
• SPINAZZE, PATRICK G.;KEAY, BRIAN A., TETRAHEDRON LETT., 30,(1989) N4, C. 1765-1768
  作者：SPINAZZE, PATRICK G.、KEAY, BRIAN A.

  DOI：——

  日期：——
• BURES, EDWARD J.;KEAY, BRIAN A., TETRAHEDRON LETT., 29,(1988) N 11, 1247-1250
  作者：BURES, EDWARD J.、KEAY, BRIAN A.

  DOI：——

  日期：——