(1S,2S)-2-Hydroxymethyl-2-methyl-cyclohexanol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,2S)-2-Hydroxymethyl-2-methyl-cyclohexanol
• 英文别名: (1S,2S)-2-(hydroxymethyl)-2-methylcyclohexan-1-ol
• 化学式: C₈H₁₆O₂
• 分子量: 144.214
• InChiKey: OXDOZKZGTKEASS-YUMQZZPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  在 palladium on activated charcoal sodium tetrahydroborate 、 硫酸 、 氢气 作用下， 以 乙醇 为溶剂， 反应 7.0h， 生成 (1S,2S)-2-Hydroxymethyl-2-methyl-cyclohexanol
  参考文献：
  名称：

  有机合成中的糖有机底物。水溶性丁二烯基醚的制备及其在水性环加成中的用途。

  摘要：

  合成了以游离葡萄糖为亲水部分的手性水溶性丁二烯基醚，并与甲基丙烯醛进行水环加成反应，通过纯内过渡态提供只有两种非对映异构体，可通过酶促水解除去糖。

  DOI：

  10.1016/s0040-4039(00)98127-9

文献信息

• Stereochemical variations in aqueous cycloadditions using glyco-organic substrates as a consequence of chemical manipulations on the sugar moiety.
  作者：André Lubineau、Yves Queneau

  DOI：10.1016/s0040-4020(01)89140-7

  日期：1989.1

  in dienyl glycosidesallowed us to rationalize the stereochemistry of our aqueouscycloadditions using glyco-organic substrates. In this way, several dienyl glucosides having benzyl group in 2 or 6 position of the sugar gave a stereofacial selectivity which could beanticipated. Finally, aqueous cycloaddition of 2-methyl butadienyl α-D-glucoside with methacrolein gave a mixture ofadducts in which the major

  二烯基糖苷中糖部分的化学修饰使我们能够使用糖-有机底物合理化水性环加成反应的立体化学。以这种方式，在糖的2或6位具有苄基的几种二烯基葡糖苷给出了可以预期的立体界面选择性。最后，将2-甲基丁二烯基α-D-葡萄糖苷与甲基丙烯醛进行水环加成反应，得到加合物的混合物，其中主要的非对映异构体endo-Re以18:82的立体界面选择性和20：1的endo-exo比率得到78％的收率。 。
• 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.
• 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.