(1R*,2S*)-1-cyclohexyl-2-methyl-1,3-bis(trimethylsiloxy)propane | 135067-18-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (1R*,2S*)-1-cyclohexyl-2-methyl-1,3-bis(trimethylsiloxy)propane
• CAS: 135067-18-4
• 化学式: C₁₆H₃₆O₂Si₂
• 分子量: 316.632
• InChiKey: ZQOOXCAMFVBHJC-GDBMZVCRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.27
• 重原子数：
  20.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (1R*,2S*)-1-cyclohexyl-2-methyl-1,3-bis(trimethylsiloxy)propane 在 sodium hydroxide 、 草酰氯 、 三氟甲磺酸三甲基硅酯 、 对甲苯磺酸 、 silver nitrate 、 二甲基亚砜 、 三乙胺 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 23.67h， 生成 (2R,3R)-3-cyclohexyl-3-hydroxy-2-methylpropanoic acid
  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 、 三氟甲磺酸三甲基硅酯 、 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 51.0h， 生成 (1R*,2S*)-1-cyclohexyl-2-methyl-1,3-bis(trimethylsiloxy)propane
  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

• 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。
• Enantiodifferentiating transformation of prochiral 1,3,5-pentanetriols controlled by intramolecular van der Waals attractions
  作者：Toshiro Harada、Isao Wada、Jun-ji Uchimura、Atsushi Inoue、Sachi Tanaka、Akira Oku

  DOI：10.1016/s0040-4039(00)92049-5

  日期：1991.2

  Acetalization of prochiral 1,3,5-pentanetriol derivatives (5) with l-menthone proceeded enantioselectively (3.0-4.6:1) to give chiral spiroacetals (6) which can be utilized as versatile chiral building blocks.
• Harada, Toshiro; Inoue, Atsushi; Wada, Isao, Journal of the American Chemical Society, 1993, vol. 115, # 17, p. 7665 - 7674
  作者：Harada, Toshiro、Inoue, Atsushi、Wada, Isao、Uchimura, Jun-Ji、Tanaka, Sachi、Oku, Akira

  DOI：——

  日期：——
• A highly convergent asymmetric synthesis of the C(19)-C(27) segment of rifamycin S: an application of enantiodifferentiating acetalization with menthone
  作者：Toshiro Harada、Yasuhiro Kagamihara、Sachi Tanaka、Kazuhiko Sakamoto、Akira Oku

  DOI：10.1021/jo00032a004

  日期：1992.3

  An enantiodifferentiating transformation of 1,3-alkanediols by kinetic acetalization with menthone is developed and used in a highly convergent asymmetric synthesis of the C(19)-C(27) segment of the ansa chain of rifamycin S.