(1S,2S)-2-acetoxy-1-methyl-3-cyclohexenecarbaldehyde | 155976-18-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,2S)-2-acetoxy-1-methyl-3-cyclohexenecarbaldehyde
• 英文别名: 3-Cyclohexene-1-carboxaldehyde, 2-(acetyloxy)-1-methyl-, (1S-trans)-；[(1S,6S)-6-formyl-6-methylcyclohex-2-en-1-yl] acetate
• CAS: 155976-18-4
• 化学式: C₁₀H₁₄O₃
• 分子量: 182.219
• InChiKey: JBIUCCOQANAWJI-VHSXEESVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.47
• 重原子数：
  13.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  2-甲基丙烯醛 、 1-乙酰氧基-1,3-丁二烯 在 二异丙氧基二氯化钛 、 (R)-1,1'-Bi-2-naphthol 作用下， 以 甲苯 为溶剂， 反应 18.0h， 生成 (1R,2S)-2-acetoxy-1-methyl-3-cyclohexenecarbaldehyde 、 (1S,2R)-2-acetoxy-1-methyl-3-cyclohexenecarbaldehyde 、 (1S,2S)-2-acetoxy-1-methyl-3-cyclohexenecarbaldehyde
  参考文献：
  名称：

  Asymmetric Catalysis of Diels-Alder Cycloadditions by an MS-Free Binaphthol-Titanium Complex: Dramatic Effect of MS, Linear vs Positive Nonlinear Relationship, and Synthetic Applications

  摘要：

  Asymmetric Diels-Alder (D.-A.) reaction of 5-hydroxynaphthoquinone (juglone) with butadienyl acetate catalyzed by the binaphthol-derived chiral titanium (BINOL-Ti) complex 1 proceeds in only 9% ee in the presence of molecular sieves (MS). Remarkably, however, this reaction proceeds in 76-96% ee with BINOL-Ti complex 1 freed from MS to provide the endo-adducts useful for the synthesis of anthracyclines and tetracyclines. The solid MS-free BINOL-Ti complex 1 is stable for months at -20 degrees C, Enhancements in endo selectivity and asymmetric induction are observed with the MS-free BINOL-Ti 1 also in the catalyzed D.-A. cycloaddition of methacrolein and glyoxylate with 1,3-dienol ethers and esters. The glyoxylate adducts can be converted to the mevinolin (compactin) intermediates. Surprisingly, the MS-free complex 1 exhibits not only a linear relationship between the ee's of BINOL-Ti 1 and the D.-A. products but also a positive nonlinear effect (asymmetric amplification), depending simply on the mixing manner of (R)-1 with (S)-1 or (+/-)-1.

  DOI：

  10.1021/ja00086a014