c-2-(Trimethylsiloxy)-t-2-vinyl-r-1-cyclopropancarbonsaeure-methylester | 80737-58-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: c-2-(Trimethylsiloxy)-t-2-vinyl-r-1-cyclopropancarbonsaeure-methylester
• 英文别名: methyl (1S,2S)-2-ethenyl-2-trimethylsilyloxycyclopropane-1-carboxylate
• CAS: 80737-58-2
• 化学式: C₁₀H₁₈O₃Si
• 分子量: 214.337
• InChiKey: MKSSKEQKYSLVRO-PSASIEDQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.96
• 重原子数：
  14.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  2-三甲基硅氧基-1,3-丁二烯 、 重氮乙酸甲酯 在 (4S)-4-tert-butyl-2-[2-[(4S)-4-tert-butyl-4,5-dihydro-1,3-oxazol-2-yl]propan-2-yl]-4,5-dihydro-1,3-oxazole;copper(1+);trifluoromethanesulfonate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 0.5h， 生成 methyl (1R,2R)-2-ethenyl-2-trimethylsilyloxycyclopropane-1-carboxylate 、 methyl (1S,2R)-2-ethenyl-2-trimethylsilyloxycyclopropane-1-carboxylate 、 t-2-(Trimethylsiloxy)-c-2-vinyl-r-1-cyclopropancarbonsaeure-methylester 、 c-2-(Trimethylsiloxy)-t-2-vinyl-r-1-cyclopropancarbonsaeure-methylester
  参考文献：
  名称：

  Screening of Various Catalysts for the Asymmetric Cyclopropanation of Structurally Typical Silyl Enol Ethers—Scope and Limitations of Evans's Bisoxazoline Copper Catalyst

  摘要：

  AbstractThe scope and limitations of asymmetric syntheses of 2‐siloxycyclopropanecarboxylates 3 were examined by combination of structurally typical silyl enol ethers and methyl diazoacetate with various chiral catalysts. It was found that the Schiff base complex 5ṁCu(OAc)2 and the bisoxazoline complex 6ṁCuOTf gave the highest stereoselectivities (e.g., 72% ee for cis‐3d with 5ṁCu(OAc)2 as catalyst or 76% and 73% ee for cis‐ and trans‐3a, respectively, with 6‐CuOTf as catalyst). High enantioselectivities or diastereoselectivities were obtained. Other catalysts based on copper, rhodium or ruthenium complexes afforded significantly lower values. In further investigations, Evans's bisoxazoline complex 6‐CuOTf proved to be limited to 1,1‐disubstituted silyl enol ethers (e.g. 1a and 1e) for high enantiomeric excesses (up to > 95%, poor diastereoselectivities) and to 1,2‐substituted enol ethers (e.g. 1e) for high diastereoselectivities (cis:trans < 3:97, eetrans = 49%).

  DOI：

  10.1002/chem.19970030418