(E)-(2R,3S)-2-Hydroxy-3-(dimethylphenylsilyl)-4-hexenoic acid | 133323-23-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (E)-(2R,3S)-2-Hydroxy-3-(dimethylphenylsilyl)-4-hexenoic acid
• 英文别名: (E,2R,3S)-3-[dimethyl(phenyl)silyl]-2-hydroxyhex-4-enoic acid
• CAS: 133323-23-6
• 化学式: C₁₄H₂₀O₃Si
• 分子量: 264.397
• InChiKey: FKCJUPGASBNTKV-KMEVASEGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.99
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (E)-(2S,3R)-2-((tert-Butyldiphenylsilyl)oxy)-3-(dimethylphenylsilyl)-4-hexenoic acid 、 (E)-(2R,3R)-2-((tert-Butyldiphenylsilyl)oxy)-3-(dimethylphenylsilyl)-4-hexenoic acid 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 (E)-(2R,3S)-2-Hydroxy-3-(dimethylphenylsilyl)-4-hexenoic acid
  参考文献：
  名称：

  Claisen rearrangements of enantiomerically pure C3-(acyloxy)-(E)-vinylsilanes

  摘要：

  The Ireland ester Claisen rearrangement of chiral (R)- and (S)-C3-(acyloxy)-(E)-vinylsilanes gives access to a wide range of alpha-chiral-beta-silyl-(E)-hexenoic acids with useful levels of diastereoselectivity for both the 2,3-syn and 2,3-anti diastereomers as illustrated in eqs 1 and 2. The vicinal diastereoselectivities for simple propionate esters rac-1b, (S)-1e, and (R)-1g can be varied from 1:12 to 16:1 (syn:anti) depending on reaction conditions. The employment of appropriately protected glycolate esters yields Claisen products with diastereoselectivities ranging from 23:1 (syn:anti), resulting from chelation control of enolate geometry, to 1:3.6 (syn:anti) via the use of a nonchelating, silicon-protecting group. The reaction of alpha-azido acetate (R)-1i is the first example of a Claisen rearrangement involving an alpha-azido ester and results in a new approach toward the asymmetric synthesis of alpha-amino acids. The assignment of relative stereochemistry based on the vicinal coupling constant data has been well documented.

  DOI：

  10.1021/jo00010a046

文献信息

• Claisen rearrangements of enantiomerically pure C3-(acyloxy)-(E)-vinylsilanes
  作者：Michelle A. Sparks、James S. Panek

  DOI：10.1021/jo00010a046

  日期：1991.5

  The Ireland ester Claisen rearrangement of chiral (R)- and (S)-C3-(acyloxy)-(E)-vinylsilanes gives access to a wide range of alpha-chiral-beta-silyl-(E)-hexenoic acids with useful levels of diastereoselectivity for both the 2,3-syn and 2,3-anti diastereomers as illustrated in eqs 1 and 2. The vicinal diastereoselectivities for simple propionate esters rac-1b, (S)-1e, and (R)-1g can be varied from 1:12 to 16:1 (syn:anti) depending on reaction conditions. The employment of appropriately protected glycolate esters yields Claisen products with diastereoselectivities ranging from 23:1 (syn:anti), resulting from chelation control of enolate geometry, to 1:3.6 (syn:anti) via the use of a nonchelating, silicon-protecting group. The reaction of alpha-azido acetate (R)-1i is the first example of a Claisen rearrangement involving an alpha-azido ester and results in a new approach toward the asymmetric synthesis of alpha-amino acids. The assignment of relative stereochemistry based on the vicinal coupling constant data has been well documented.