(1R*,2R*,3R*)-2,4-Dimethyl-1-phenylpentan-1,3-diol | 116047-23-5

• 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: (1R*,2R*,3R*)-2,4-Dimethyl-1-phenylpentan-1,3-diol
• 英文别名: 1-phenyl-2,4-dimethylpentane-1,3-diol；(1S,2R,3S)-2,4-dimethyl-1-phenylpentane-1,3-diol
• CAS: 116047-23-5；116126-89-7；116126-91-1；116126-92-2
• 化学式: C₁₃H₂₀O₂
• 分子量: 208.301
• InChiKey: JEXZPZDZEAHDKZ-WXHSDQCUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 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*,2R*,3R*)-2,4-Dimethyl-1-phenylpentan-1,3-diol 、 苯硼酸 在 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 以98%的产率得到(4R*,5R*,6R*)-4-Isopropyl-5-methyl-2,6-diphenyl-1,3,2-dioxaborinane
  参考文献：
  名称：

  The Role of theα-Stereogenic Center in the Control of Stereoselection in the Reduction ofα-Alkyl-β-hydroxy Ketones: A Highly Diastereoselective Protocol for the Synthesis of 1,2-syn-2-Alkyl-1,3-diols

  摘要：

  Accurate investigations on the role played by an alpha-stereogenic center in controlling the reduction of various classes of beta-hydroxy ketones allowed us to set up a general and highly diastereoselective protocol for the synthesis of 2-alkyl-1,3-diols with 1,2-syn relationship. This methodology is based on the conversion of a beta-hydroxy ketone into the corresponding titanium alcoholate that permits us to organize the substrate in a stable and rigid structure, which stereofacially favors attacking hydride ions. The use of THF as solvent makes available a variety of hydride donors that cover a large spectrum of steric demand: the choice of the more appropriate one depends on the conformational stability of the cyclic intermediate. Excellent results are obtained also in the presence of an additional stereogenic center in the beta-position, even if it exerts a concordant or an opposite steric effect with respect to the alpha-substituent.

  DOI：

  10.1002/1521-3765(20000717)6:14<2590::aid-chem2590>3.0.co;2-x
• 作为产物：
  描述：

  [2R,3S,1'S,2'S]-(+)-(2'-hydroxy-1'-methyl-2'-phenylethyl)-3-hydroxy-N,2,5-trimethylpentanamide 在 dimethyl sulfide borane 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.67h， 生成 (1R*,2R*,3R*)-2,4-Dimethyl-1-phenylpentan-1,3-diol
  参考文献：
  名称：

  使用基于（S，S）-（+）-伪麻黄碱的酰胺的不对称羟醛反应：立体选择性合成α-甲基-β-羟基酸，酯，酮以及1,3-Syn和1,3-抗二醇

  摘要：

  报道了进行立体选择性醛醇缩合反应的非常有效的方法。（S，S）-（+）-伪麻黄碱衍生的丙酰胺烯醇化物与几种醛的反应仅以良好的收率仅产生了四种可能的非对映异构体之一，尽管先生成的烯醇酸锂与锆（​​II）盐进行了重金属化。为了获得高的顺式选择性，添加醛是必需的。如此形成的顺-α-甲基-β-羟基酰胺被转化为其他有价值的手性非外消旋合成子，例如α-甲基-β-羟基酸，酯和酮。最后，已经开发了一种立体控制的还原程序，该程序从如此获得的α-甲基-β-羟基酮开始，可以合成1,3-syn-或1,3-抗-α-甲基-1，

  DOI：

  10.1021/jo000035h

文献信息

• 1,2-anti diastereoselective reduction of 2-alkyl-3-hydroxy-ketones via their silyl ethers
  作者：R. Bloch、L. Gilbert、C. Girard

  DOI：10.1016/0040-4039(88)85324-3

  日期：1988.1

  T-butyldimethylsilyl ethers of a range of acyclic 2-alkyl-3-hydroxy-ketones are reduced with lithium aluminum hydride to give with a high 1,2-anti diastereoselective induction syn,anti or anti,anti 2-alkyl-1,3-diols.

  用氢化铝锂还原一系列无环2-烷基-3-羟基酮的叔丁基二甲基甲硅烷基醚，得到具有高1,2-抗非对映选择性诱导的顺，反或反2-烷基-1,3 -二醇。
• Tandem Aldol-Reduction Reaction of Dimethylsilyl Enolates: A New Method for Stereoselective Preparation of 1,3-Diols
  作者：Katsukiyo Miura、Takahiro Nakagawa、Shuntaro Suda、Akira Hosomi

  DOI：10.1246/cl.2000.150

  日期：2000.2

  derived from acyclic ketones reacted with aldehydes to give syn,syn-1,3-diols 7a and 8a with moderate to high diastereoselectivity. The stereochemical outcome can be attributed to a syn-selective aldol reaction and the subsequent 1,2-syn-selective intramolecular reduction.

  在催化量的 TBAF (Bu4NF) 存在下，衍生自无环酮的二甲基甲硅烷基烯醇化物与醛反应，得到具有中高非对映选择性的 syn,syn-1,3-二醇 7a 和 8a。立体化学结果可归因于顺式选择性羟醛反应和随后的 1,2-顺式选择性分子内还原。
• BCl₃- and TiCl₄-Mediated Reductions of β-Hydroxy Ketones
  作者：Christopher R. Sarko、Scott E. Collibee、Allison L. Knorr、Marcello DiMare

  DOI：10.1021/jo951549x

  日期：1996.1.1

  Syn-selective reduction protocols for beta-hydroxy ketones are described exploiting the intermediacy of titanium and boron chelates derived from TiCl4 and BCl3, respectively, Reductions are conducted at -78 degrees C in CH2Cl2 using a wide range of CH2Cl2-soluble reducing agents, Added acid-scavenging agents are detrimental to reaction selectivity, An A((1,3))-like interaction involving the stereocenter responsible for asymmetric induction provides conformational biasing of the intermediate chelates necessary for high diastereoselectivity.
• Simple Metal Alkoxides as Effective Catalysts for the Hetero-Aldol−Tishchenko Reaction
  作者：Cheryl M. Mascarenhas、Matthew O. Duffey、Shih-Yuan Liu、James P. Morken

  DOI：10.1021/ol990246c

  日期：1999.11.1

  [GRAPHICS]This paper reports the utility of simple metal alkoxides for the catalytic, stereoselective hetero-aldol-Tishchenko reaction (eq 1), Choice of metal alkoxide is crucial to achieving high efficiency and stereoselectivity, Whereas NaO-t-Bu is an effective catalyst, delivering one product in 68% yield and 99:1 stereoselection, Sm(O-i-Pr)(3) is less effective and delivers the same product in 42% yield with 4:1 stereoselection.
• Tandem Aldol−Tishchenko Reactions of Lithium Enolates:  A Highly Stereoselective Method for Diol and Triol Synthesis
  作者：Paul M. Bodnar、Jared T. Shaw、K. A. Woerpel

  DOI：10.1021/jo971012e

  日期：1997.8.1