(S)-3-methyl-2-phenylbutane-1,2-diol | 51559-18-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-3-methyl-2-phenylbutane-1,2-diol
• 英文别名: (2S)-3-methyl-2-phenylbutane-1,2-diol
• CAS: 51559-18-3
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: HEYRHDCXPZCMNV-NSHDSACASA-N

物化性质

• 沸点：
  319.2±22.0 °C(Predicted)
• 密度：
  1.072±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  (S)-3-methyl-2-phenylbutane-1,2-diol 以95%的产率得到(S)-(+)-2-hydroxy-2-phenyl-3-methylbutyraldehyde
  参考文献：
  名称：

  .alpha.-Hydroxyaldehyde and a process for preparing the same

  摘要：

  一种光学活性或拉氏体的α-羟基醛，由通式（2）表示，其中R₁代表C₆-C₁₄芳基、C₁-C₁₀烷基、C₃-C₁₀烯基、C₂-C₁₀炔基、C₇-C₁₄芳基烷基或含有有机部分中的官能团的基团，R₂代表C₁-C₁₀烷基、C₂-C₁₀烯基、C₂-C₁₀炔基、C₇-C₁₄芳基烷基、C₆-C₁₄芳基或含有这些基团的有机部分中的官能团的基团，这是制备药物和农药的重要中间体，通过让通式（1）表示的光学活性或拉氏体化合物（其中A代表C₆-C₁₄芳基或C₁-C₄烷基或烷氧基-或卤素取代的C₆-C₁₄芳基，R₁如上定义）与格氏试剂反应，然后水解反应产物制备而成。

  公开号：

  US04337346A1
• 作为产物：
  描述：

  (1S,2R,3S,5R,2'S)-6,6-dimethyl-3-(2'-ethoxy-1'-phenyl-1'-oxo-2'-ethylsulfanyl)-2-(O-t-butyl-dimethylsilyl-hydroxymethyl)-bicyclo[3.1.1]heptane 在 N-氯代丁二酰亚胺 、 silver nitrate 作用下， 生成 (S)-3-methyl-2-phenylbutane-1,2-diol
  参考文献：
  名称：

  New S,O-acetals from (1R)-(−)-myrtenal as chiral auxiliaries in nucleophilic additions

  摘要：

  Treatment of hydroxythiol 4 with alpha,alpha-diethoxyacetophenone at room temperature yielded a mixture of epimeric S,O-acetals 6 and 7 (1:4. 92%, yield), which were efficiently separated by flash chromatography. The OTBS derivatives 8 and 9 were treated with several Grignard reagents to afford carbinols 10 and 13 respectively (85-99%, yield, >95% dr). After successive hydrolysis and reduction of 10 and 13 it is possible to obtain either enantiomer of diols 16 in high optical purity (>95% er). (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.01.046

文献信息

• Electronic polarizability-based stereochemical model for Sharpless AD reactions
  作者：Peng Han、Ruji Wang、David Zhigang Wang

  DOI：10.1016/j.tet.2011.09.073

  日期：2011.11

  controlling absolute stereochemical courses of general asymmetric induction events. Thus, a sensitive dependence of the sense of chiral induction on an alkene substrate’s substituent electronic polarizability character was uncovered from a range of structurally highly comparable Sharpless asymmetric dihydroxylation (AD) systems, from which a new polarizability-based stereochemical model of predictive power

  柔软确实是力量！此处报道的是电子极化率（即柔软度）效应在控制一般不对称诱导事件的绝对立体化学过程中的关键但长期被忽视的作用。因此，从一系列结构上高度可比的Sharpless不对称二羟基化（AD）系统中发现了手性诱导感对烯烃底物的取代基电子极化率特征的敏感依赖性，从中提出了基于极化率的基于立体化学的新预测能力模型。
• Enecarbamates as Selective Substrates in Oxidations:  Chiral-Auxiliary-Controlled Mode Selectivity and Diastereoselectivity in the [2+2] Cycloaddition and Ene Reaction of Singlet Oxygen and in the Epoxidation by DMD and <i>m</i>CPBA
  作者：Waldemar Adam、Sara G. Bosio、Nicholas J. Turro、Barbara T. Wolff

  DOI：10.1021/jo035745c

  日期：2004.3.1

  The stereochemical course of the oxidation of chiral oxazolidinone-substituted enecarbamates has been studied for singlet oxygen (1O2), dimethyldioxirane (DMD), and m-chloroperbenzoic acid (mCPBA) by examining of the special structural and stereoelectronic features of the enecarbamates. Valuable mechanistic insight into these selective oxidations is gained. Whereas the R1 substituent on the chiral

  手性恶唑烷酮取代enecarbamates氧化的立体化学过程已经研究了单重态氧（1 Ò 2），二甲基二（DMD），和中号氯过苯甲酸（米通过的enecarbamates的特殊的结构和立体电子特征检查CPBA） 。获得了对这些选择性氧化的有价值的机理见解。而手性助剂上的R 1取代基负责双键的空间屏蔽，并决定π面非对映选择性的感觉，Z / E构型等结构特征和R 2的性质双键上的基团负责非对映选择性的程度。在1 O 2的情况下，通过乙烯基氮官能团进行的立体电子控制可控制模式选择性（烯反应与[2 + 2]环加成反应）。
• Construction of a quaternary carbon center via cyclic sulfite
  作者：Nanae Nishimura、Oyo Mitsunobu

  DOI：10.1016/s0040-4039(00)00315-4

  日期：2000.4

  Reaction of (S)-2-oxo-4-methyl-4-phenyl-1,3,2-dioxathiolane with triethylaluminum selectively took place at the tertiary carbinol center to give (R)-2-methyl-2-phenyl-1-butanol. Enhanced stereoselectivity was obtained in a nonpolar solvent. Similarly, a series of (S)-4,4-disubstituted-1,3,2-dioxathiolanes reacted with trimethylaluminum to afford the corresponding (R)-2-alkyl-2-phenyl-1-propanols in

  （S）-2-氧代-4-甲基-4-苯基-1,3,2-二氧杂硫杂环戊烷与三乙基铝的反应在叔甲醇中心选择性地发生，得到（R）-2-甲基-2-苯基-1 -丁醇。在非极性溶剂中获得增强的立体选择性。类似地，一系列（S）-4，4-二取代-1，3，2-二氧杂硫杂环戊烷与三甲基铝反应以良好的产率得到相应的（R）-2-烷基-2-苯基-1-丙醇。
• Resolution of Diols via Catalytic Asymmetric Acetalization
  作者：Ji Hye Kim、Ilija Čorić、Chiara Palumbo、Benjamin List

  DOI：10.1021/ja512481d

  日期：2015.2.11

  A highly enantioselective kinetic resolution of diols via asymmetric acetalization has been achieved using a chiral confined imidodiphosphoric acid catalyst. The reaction is highly efficient for the resolution of tertiary alcohols, giving selectivity factors of up to >300. Remarkably, even in cases where the selectivity factors are only moderate, highly enantioenriched diols are obtained via a stereodivergent

  使用手性限制的亚氨基二磷酸催化剂，通过不对称缩醛化实现了二醇的高度对映选择性动力学拆分。该反应对叔醇的拆分非常有效，选择性因子高达 >300。值得注意的是，即使在选择性因素仅为中等的情况下，高度对映体丰富的二醇也是通过立体发散拆分非对映缩醛获得的。
• Camphor-derived 2-stannyl-N-Boc-1,3-oxazolidine: A new chiral formylanion equivalent for the asymmetric synthesis of 1,2-diols
  作者：Lino Colombo、Marcello Di Giacomo、Gloria Brusotti、Ettore Milano

  DOI：10.1016/0040-4039(95)00369-n

  日期：1995.4

  3-oxazolidine 6, prepared from the camphor-derived aminoalcohol 5, was converted to diastereomerically pure 2-acyl derivatives 8 in three steps. Reaction of these ketones with Grignard reagents at −78°C proceeded with high stereoselectivity affording tertiary carbinols which gave 1,2-diols with >96% ee after hydrolysis and reduction of the intermediate α-hydroxy aldehydes. A new deblocking procedure of the

  由樟脑衍生的氨基醇5制备的光学纯的2-三丁基锡烷基-N-Boc-1,3-恶唑烷6经三步转化为非对映体纯的2-酰基衍生物8。这些酮与格氏试剂在-78℃下的反应以高的立体选择性进行，得到叔甲醇，其在水解和还原中间的α-羟基醛后，得到具有> 96％ee的1,2-二醇。还描述了t-Boc组的新解块过程。