(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.
• Glyco-organic substrates in organic synthesis. Preparation of a water soluble butadienyl-ether and its use in aqueous cycloaddition.
  作者：Andrè Lubineau、Yves Queneau

  DOI：10.1016/s0040-4039(00)98127-9

  日期：1985.1

  A chiral water-soluble butadienyl-ether containing free glucose as hydrophilic moiety was synthesized and used in aqueous cycloaddition reaction with methacrolein to afford through pure endo transition state, only two diastereoisomers from which the sugar could be removed by enzymatic hydrolysis.

  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。