(1R,2S)-2-acetoxy-1-methyl-3-cyclohexenecarbaldehyde | 137037-08-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,2S)-2-acetoxy-1-methyl-3-cyclohexenecarbaldehyde
• 英文别名: [(1S,6R)-6-formyl-6-methylcyclohex-2-en-1-yl] acetate
• CAS: 137037-08-2
• 化学式: C₁₀H₁₄O₃
• 分子量: 182.219
• InChiKey: JBIUCCOQANAWJI-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1R,2S)-2-acetoxy-1-methyl-3-cyclohexenecarbaldehyde 在 palladium on activated charcoal lithium aluminium tetrahydride 、 氢气 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 2.0h， 生成 (1S,2S)-2-Hydroxymethyl-2-methyl-cyclohexanol
  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
• 作为产物：
  描述：

  2-甲基丙烯醛 、 1-乙酰氧基-1,3-丁二烯 在 对苯二酚 作用下， 以 甲苯 为溶剂， 反应 10.0h， 以70%的产率得到(1R,2S)-2-acetoxy-1-methyl-3-cyclohexenecarbaldehyde
  参考文献：
  名称：

  Diels–Alder途径开发潜在的三茂茂前体

  摘要：

  2-甲基丁-3-yn-2-ol（9）有效地转化为6-甲酰基-3,6-二甲基环己-2-烯基乙酸酯（4b）和6-乙酰基3,6-二甲基环己-2-烯基通过高度区域选择性和立体选择性的Diels-Alder环加成乙酸3-甲基丁酯1，，3-二烯基乙酸酯（2b）生成乙酸酯（4c ）。环加合物（4b）被碱转化为4a，5,6,8a-四氢-4a，7-二甲基香豆素（13b），而环加合物（4c）产生2,3,4a，5,6,8a-六氢- 2-羟基-2,4a，7-三甲基苯并吡喃-4-酮（15），其结构通过X射线分析证实。（13b）和（15）都具有单端孢菌烯的许多结构特征，并且可能在它们的总合成中具有价值。

  DOI：

  10.1039/p19810001096

文献信息

• Diazepane Carboxylates as Organocatalysts in the Diels-Alder Reaction of α-Substituted Enals
  作者：Nicklas O. Häggman、Benjamin Zank、HyunJune Jun、Dainis Kaldre、James L. Gleason

  DOI：10.1002/ejoc.201801009

  日期：2018.10.24

  Diazepane carboxylates efficiently catalyze the Diels–Alder cycloaddition of α‐substituted enals with a range of dienes. With chiral diazepane backbones, weak electrostatic interactions favour diene approach from the more hindered face, leading to enantioselectivities of 70–95 % with a range of dienophiles.

  地西羧酸盐可有效催化α-取代的烯类与一系列二烯的狄尔斯-阿尔德环加成反应。对于手性二氮杂庚烷骨架，较弱的表面会产生弱的静电相互作用，从而有利于二烯方法，导致一系列亲二烯体的对映选择性为70–95％。
• 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.