(1S,2R)-2-methoxy-1-methyl-3-cyclohexenecarbaldehyde | 112622-13-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,2R)-2-methoxy-1-methyl-3-cyclohexenecarbaldehyde
• 英文别名: (1S,2R)-2-methoxy-1-methylcyclohex-3-ene-1-carbaldehyde
• CAS: 112622-13-6；130156-79-5；130881-22-0；137037-07-1
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: SKYDAELNGJWNTN-RKDXNWHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.56
• 重原子数：
  11.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  2-甲基丙烯醛 、 1-甲氧基-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 2.0h， 生成 1-methyl-2-methoxy-3-cyclohexene-1-carboxaldehyde 、 (1S,2R)-2-methoxy-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

文献信息

• Chiral titanium complex-catalyzed Diels-Alder reaction: A practical route to anthracycline intermediates
  作者：Koichi Mikami、Masahiro Terada、Yukihiro Motoyama、Takeshi Nakai

  DOI：10.1016/s0957-4166(00)86118-2

  日期：1991.1

  Asymmetric Diels-Alder reactions of methacrolein and 1,4-naphthoquinone with 1,3-dienol derivatives catalyzed by the chiral binaphthol (BINOL)-derived titanium complex 1 are shown to provide the corresponding endo-adducts in high enantiomeric purity. The naphthoquinone adduct can serve as a synthetic intermediate of tetracycline antibiotics.
• 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
  作者：Koichi Mikami、Yukihiro Motoyama、Masahiro Terada

  DOI：10.1021/ja00086a014

  日期：1994.4

  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.