triisopropylsilyl β-methylcrotonate | 1211543-86-0

• 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: triisopropylsilyl β-methylcrotonate
• 英文别名: triisopropylsilyl 3-methylcrotonate
• CAS: 1211543-86-0
• 化学式: C₁₄H₂₈O₂Si
• 分子量: 256.461
• InChiKey: AYZXLNIKUWKMAE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.67
• 重原子数：
  17.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  三异丙基氯硅烷 、 triisopropylsilyl β-methylcrotonate 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 3.33h， 以73%的产率得到1,1-bis(triisopropylsiloxy)-3-methyl-1,3-butadiene
  参考文献：
  名称：

  Selective Triisopropylsilylation of α-Amino Acids: Protection without Racemization

  摘要：

  The mono-, di- and trisilylation of alpha-amino acids with TIPSOTf is described. Treatment of the alpha-amino acids, proline and tryptophan with TIPSOTf in MeCN provides a quantitative yield of the corresponding ammonium salts of the O-TIPS esters (4). Employing two (2) equivalents of TIPSOTf/EDIPA produces N,O-bis-TIPS amino acid derivatives (2) without racemization as stable compounds (73-87%, 13 examples). Three (3) equivalents of this silylation mixture produces the corresponding tris-TIPS derivatives 6 (62-88%, 6 examples) from amino acids which contain protic functionality in their side chain. While this trisilylation procedure is ineffective for tryptophan, the N,O-bis-TIPS derivative 2m is easily prepared through this method, and the third silylation is achieved without racemization employing t-BuLi/R3SiX producing N-1-SiR3-N,O-bis-TIPS tryptophans (51-97%, 4 examples).

  DOI：

  10.3987/com-09-s(s)37
• 作为产物：
  描述：

  3,3-二甲基丙烯酸 、 三异丙基氯硅烷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 以80%的产率得到triisopropylsilyl β-methylcrotonate
  参考文献：
  名称：

  Selective Triisopropylsilylation of α-Amino Acids: Protection without Racemization

  摘要：

  The mono-, di- and trisilylation of alpha-amino acids with TIPSOTf is described. Treatment of the alpha-amino acids, proline and tryptophan with TIPSOTf in MeCN provides a quantitative yield of the corresponding ammonium salts of the O-TIPS esters (4). Employing two (2) equivalents of TIPSOTf/EDIPA produces N,O-bis-TIPS amino acid derivatives (2) without racemization as stable compounds (73-87%, 13 examples). Three (3) equivalents of this silylation mixture produces the corresponding tris-TIPS derivatives 6 (62-88%, 6 examples) from amino acids which contain protic functionality in their side chain. While this trisilylation procedure is ineffective for tryptophan, the N,O-bis-TIPS derivative 2m is easily prepared through this method, and the third silylation is achieved without racemization employing t-BuLi/R3SiX producing N-1-SiR3-N,O-bis-TIPS tryptophans (51-97%, 4 examples).

  DOI：

  10.3987/com-09-s(s)37

文献信息

• Preparation of silyl polyenol ethers by carbonyl olefination of silyl esters
  作者：Takeshi Takeda、Tatsuya Fukada、Akira Tsubouchi

  DOI：10.1016/j.tetlet.2014.01.040

  日期：2014.2

  Silyl enol ethers were produced by the carbonyl olefination of silyl esters with titanium carbene complexes generated by the desulfurizative titanation of thioacetals. The regioselective preparation of silyl dienol and trienol ethers has been achieved by using unsaturated silyl esters and thioacetals.

  甲硅烷基烯醇醚是通过将甲硅烷基酯的羰基烯化与硫代乙缩醛的脱硫钛化反应生成的钛碳烯配合物而制得的。甲硅烷基二烯醇和三烯醇醚的区域选择性制备已经通过使用不饱和甲硅烷基酯和硫代缩醛实现。