(1R*,2S*)-1-cyclohexyl-2-methyl-1,3-propanediol | 138602-95-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R*,2S*)-1-cyclohexyl-2-methyl-1,3-propanediol
• 英文别名: anti-1-cyclohexyl-2-methylpropane-1,3-diol；(1S,2R)-1-cyclohexyl-2-methylpropane-1,3-diol
• CAS: 138602-95-6
• 化学式: C₁₀H₂₀O₂
• 分子量: 172.268
• InChiKey: VYZBHLWIWOZNBP-PSASIEDQSA-N

物化性质

• 沸点：
  284.5±8.0 °C(Predicted)
• 密度：
  1.010±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  12
• 可旋转键数：
  3
• 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

• 作为反应物：
  描述：

  (1R*,2S*)-1-cyclohexyl-2-methyl-1,3-propanediol 在 三氟甲磺酸三甲基硅酯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 19.0h， 生成 (2S,3R,6R,7S,10R)-2-Cyclohexyl-7-isopropyl-3,10-dimethyl-1,5-dioxa-spiro[5.5]undecane
  参考文献：
  名称：

  Stereoselective acetalization of 1,3-alkanediols by l-menthone: application to the resolution of racemic 1,3-alkanediols and to the determination of the absolute configuration of enantiomeric 1,3-alkanediols

  摘要：

  A general and reliable method for the resolution of racemic 1,3-alkanediols, which involves their conversion into diastereomeric spiroacetals derived from l-menthone, is described. Thus, the reaction of the bis-O-trimethylsilyl derivatives of racemic 1,3-alkanediols with l-menthone in the presence of a catalytic amount of trimethylsilyl trifluoromethanesulfonate affords the diastereomeric spiroacetals 3 and 4. The two can be readily separated by silica gel column chromatography. Hydrolysis of each diastereomer under acidic conditions liberates the corresponding enantiomerically pure diol. An empirically derived correlation of configuration and H-1 NMR chemical shifts for spiroacetals 3 and 4 has been developed which is rationalized based on long-range effects due to the magnetic anisotropy inherent to the menthane ring in a rigid spiroacetal conformation. The method described here should be widely applicable to the determination of the absolute configuration of various 1,3-alkanediols.

  DOI：

  10.1021/jo00031a019
• 作为产物：
  描述：

  (+/-)-1-cyclohexyl-2-methyl-2-propen-1-ol 在 咪唑 、 sodium hydroxide 、 9-borabicyclo[3.3.1]nonane dimer 、 四丁基氟化铵 、 双氧水 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 50.0h， 生成 (1R*,2S*)-1-cyclohexyl-2-methyl-1,3-propanediol
  参考文献：
  名称：

  Stereoselective acetalization of 1,3-alkanediols by l-menthone: application to the resolution of racemic 1,3-alkanediols and to the determination of the absolute configuration of enantiomeric 1,3-alkanediols

  摘要：

  A general and reliable method for the resolution of racemic 1,3-alkanediols, which involves their conversion into diastereomeric spiroacetals derived from l-menthone, is described. Thus, the reaction of the bis-O-trimethylsilyl derivatives of racemic 1,3-alkanediols with l-menthone in the presence of a catalytic amount of trimethylsilyl trifluoromethanesulfonate affords the diastereomeric spiroacetals 3 and 4. The two can be readily separated by silica gel column chromatography. Hydrolysis of each diastereomer under acidic conditions liberates the corresponding enantiomerically pure diol. An empirically derived correlation of configuration and H-1 NMR chemical shifts for spiroacetals 3 and 4 has been developed which is rationalized based on long-range effects due to the magnetic anisotropy inherent to the menthane ring in a rigid spiroacetal conformation. The method described here should be widely applicable to the determination of the absolute configuration of various 1,3-alkanediols.

  DOI：

  10.1021/jo00031a019

文献信息

• Asymmetric synthesis using diisopropyl tartrate modified (E)- and (Z)-crotylboronates: preparation of the chiral crotylboronates and reactions with achiral aldehydes
  作者：William R. Roush、Kaori Ando、Daniel B. Powers、Alan D. Palkowitz、Ronald L. Halterman

  DOI：10.1021/ja00173a023

  日期：1990.8

  Crotylboronates undergo highly diastereo- and enantioselective reactions with aliphatic (linear or α-monobranched; 72-91% ee), aromatic and α,β-unsaturated aldehydes (55-74% ee). The reaction diastereoselectivity closely parallels the reagent isomeric purity especially for reactions performed at −78 o C. The enantioselectivity is best in toluene for all substrates except benzaldehyde where best results

  巴豆基硼酸酯与脂肪族（线性或 α-单支链；72-91% ee）、芳香族和 α,β-不饱和醛（55-74% ee）发生高度非对映选择性和对映选择性反应。反应的非对映选择性与试剂异构体纯度密切相关，特别是对于在 -78 o C 下进行的反应。对所有底物的对映选择性在甲苯中最佳，但苯甲醛除外，因为苯甲醛在 THF 中获得最佳结果。本研究中合成的 14 种高烯丙醇中有 9 种的相对和绝对立体化学是通过与 Sharpless 不对称环氧化制备的环氧醇的相关性来确定的
• Enantioselective acetalization of racemic 1,3-alkanediols with l-methone under kinetically controlled conditions
  作者：Toshiro Harada、Sachi Tanaka、Akira Oku

  DOI：10.1016/s0040-4020(01)89438-2

  日期：——

  (derived from 1) in preference to spiroacetal 4 (derived from ent-1). The kinetically controlled acetalization is applied to a novel kinetic resolution of racemic 1,3-alkanediols: Optically active diols ent-1 of 55–95 % ee are obtained when the racemic diols are allowed to react with 1.5 equiv of enol silyl ether 10 under similar conditions.

  外消旋的1,3-链烷二醇（rac -1）通过在三氟甲磺酸（10 mol％）存在下用1-甲基烯醇三甲基甲硅烷基醚（10）处理进行对映选择性缩醛化反应，从而得到热力学上较不稳定的螺缩醛3（由1衍生）。优先于螺乙缩醛4（源自eNT -1）。动力学控制缩醛化被施加到外消旋的1,3-链烷二醇的新颖动力学拆分：光学活性二醇ENT -1 55-95％ee值时的外消旋二醇使其与烯醇甲硅烷基醚1.5当量反应得到10 在相似的条件下。
• Copper-Catalyzed Stereospecific Hydroboration of Internal Allylic Alcohols
  作者：Enhui Ji、Haiwen Meng、Yue Zheng、Velayudham Ramadoss、Yahui Wang

  DOI：10.1002/ejoc.201901435

  日期：2019.11.30

  Copper‐catalyzed highly stereospecific hydroboration of internal allylic alcohols using a silyl ether transient protection strategy is reported. This in situ protection effectively avoids the preferential side reaction of free hydroxyl group with boron reagent, thus promoting hydroboration. This method provides both the anti‐ and the syn‐ diastereomers of 1,3‐diols in high level of diastereomeric ratios

  据报道，使用甲硅烷基醚瞬态保护策略，铜催化内部烯丙基醇的高度立体定向氢硼化。这种原位保护有效地避免了游离羟基与硼试剂的优先副反应，从而促进了硼氢化反应。此方法同时提供抗-和SYN在高电平非对映体比率具有官能团的耐受性良好的1,3-二醇非对映体- 。
• Domino Hydroformylation/Enantioselective Cross-Aldol Addition
  作者：Olivier Abillard、Bernhard Breit

  DOI：10.1002/adsc.200700216

  日期：2007.8.6

  A domino hydroformylation/enantioselective cross-aldol reaction sequence is reported. Starting from simple alkenes enantiomerically pure aldol addition products, which represent valuable building blocks for polypropionate construction, can be obtained in a one-pot operation.

  报道了多米诺加氢甲酰化/对映选择性交叉羟醛反应序列。从简单的烯烃开始，对映体纯的羟醛加成产物可以代表一锅操作，代表了丙酸酯构建的重要组成部分。
• The stereoselective synthesis of oxetanes; exploration of a new, Mitsunobu-style procedure for the cyclisation of 1,3-diols
  作者：Martin Christlieb、John E. Davies、Jason Eames、Richard Hooley、Stuart Warren

  DOI：10.1039/b106851b

  日期：2001.11.15

  A solution of 2-methyl-3-[1-(phenylsulfanyl)cyclohexyl]propane-1,3-diol 1 in toluene treated with triphenylphosphine, Ziram® 2 and DEAD, gave 3-methyl-2-[1-(phenylsulfanyl)cyclohexyl]oxetane 3 in 85% yield. A mechanistic study has been undertaken, optimal conditions have been found and the range of substrates for which the reaction is useful has been explored. We include the results of an X-ray study which shows that compound 33 (the oxidation product of diol 1) is a sulfone rather than a sulfoxide as previously reported.

  一种2-甲基-3-[1-(芳基硫）环己基]丙烷-1,3-二醇1在甲苯中与三苯基膦、Ziram® 2和DEAD反应，产物为3-甲基-2-[1-(芳基硫）环己基]噁烯3，产率为85%。我们进行了机理研究，找到了最佳反应条件，并探索了该反应适用的底物范围。我们还包括了一项X射线研究的结果，该研究显示化合物33（醇1的氧化产物）是磺酮而非先前报告的亚磺酸盐。