(1S,6S)-6-(hydroxymethyl)-6-methyl-2-cyclohexenol | 155907-01-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,6S)-6-(hydroxymethyl)-6-methyl-2-cyclohexenol
• 英文别名: (1S,6S)-6-(hydroxymethyl)-6-methylcyclohex-2-en-1-ol
• CAS: 155907-01-0
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: MFKNOVBFHNBQRS-YUMQZZPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,6S)-6-(hydroxymethyl)-6-methyl-2-cyclohexenol 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 生成 (1S,2S)-2-Hydroxymethyl-2-methyl-cyclohexanol
  参考文献：
  名称：

  Chiral titanium complex-catalyzed Diels-Alder reaction: A practical route to anthracycline intermediates

  摘要：

  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.

  DOI：

  10.1016/s0957-4166(00)86118-2
• 作为产物：
  描述：

  (2R,3R,4S,5R,6S)-4,5-bis((tert-butyldimethylsilyl)oxy)-6-methoxy-2-methyltetrahydro-2H-pyran-3-yl (R)-1-methyl-2-oxocyclohex-3-ene-1-carboxylate 在 cerium(III) chloride sodium tetrahydroborate 、 二异丁基氢化铝 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 7.0h， 生成 (1S,6S)-6-(hydroxymethyl)-6-methyl-2-cyclohexenol
  参考文献：
  名称：

  d-葡萄糖衍生模板上乙酰乙酸酯 α-碳的立体选择性双烷基化：在合成带有不对称季碳的对映纯环烯酮中的应用

  摘要：

  先前开发的 D-葡萄糖衍生物，即甲基 6-脱氧-2,3-二-O-(叔丁基二甲基甲硅烷基)-aD-吡喃葡萄糖苷，作为重要的立体控制元件，用于其 α-碳的非对映选择性烷基化。乙酰乙酸在 C-4 与两种类型的烷基卤化物。如此获得的带有甲基和烯丙基的双烷基化乙酰乙酸酯部分通过分子内醇醛策略有效地转化为官能化的 cycloalk-2-en-1-one 衍生物。此外，环烯酮的合成效用通过对如此获得的环戊烯酮衍生物的1，4-加成来举例说明。

  DOI：

  10.1055/s-2007-967934

文献信息

• 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.