5-(苄氧基)-2,4-二甲基-1,3-戊二醇 | 73814-76-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 5-(苄氧基)-2,4-二甲基-1,3-戊二醇
• 英文名称: (1SR,2RS)-1-[(1SR)-2-(benzyloxy)-1-methylethyl]-2-methylpropane-1,3-diol
• 英文别名: (2RS,3SR,4RS)-1-O-benzyl-2,4-dimethyl-1,3,5-pentanetriol；(2R,3S,4R)-2,4-dimethyl-5-phenylmethoxypentane-1,3-diol
• CAS: 73814-76-3；73837-44-2；79027-32-0；81520-10-7；81520-11-8；98167-13-6；102210-04-8；102210-06-0；103729-90-4；105816-26-0；108393-28-8；108393-30-2；145514-07-4
• 化学式: C₁₄H₂₂O₃
• 分子量: 238.327
• InChiKey: IWLHKVFTKXOSID-BZPMIXESSA-N

物化性质

• 沸点：
  389.1±32.0 °C(Predicted)
• 密度：
  1.064±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5-(苄氧基)-2,4-二甲基-1,3-戊二醇 在 三乙胺 、 sodium iodide 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 6.0h， 生成 (2SR,3RS,4RS)-5-O-benzyl-1-iodo-2,4-dimethyl-3,5-pentanediol
  参考文献：
  名称：

  Stereoselective total synthesis of (.+-.)-invictolide. An efficient preparation of a trisubstituted .delta.-lactone from aldol precursors

  摘要：

  The stereoselective total synthesis of (+/-)-invictolide (1), a component of the queen recognition pheromone of Solenopsis invicta, is described. The TiCl4-mediated addition of silyl ketene thioacetal 8 to (+/-)-3-(benzyloxy)-2-methylpropionaldehyde afforded exclusively thioester 10, in 65% yield, which was straightforwardly converted to diol 5 (ca. 31% yield). Diol 5 was also prepared after LiAlH4 reduction of the major aldol formed in the condensation between the lithium enolate of 2,6-di-tert-butyl-4-methylphenyl propanoate and (+/-)-2-methylvaleraldehyde (ca.50% overall yield). Intramolecular alkylation (t-BuOK-THF) of 6 or 7 gave a 40:60 mixture of (+/-)-1 and its C(3) epimer. Catalytic hydrogenation of unsaturated lactone 17 afforded (+/-)-1 in 80% yield.

  DOI：

  10.1021/jo00054a014
• 作为产物：
  描述：

  S-tert-butyl (2S,3R,4R)-3-hydroxy-2,4-dimethyl-5-phenylmethoxypentanethioate 在 Raney-Ni W₁ 、 氢气 作用下， 以 甲醇 为溶剂， 反应 0.5h， 以70%的产率得到5-(苄氧基)-2,4-二甲基-1,3-戊二醇
  参考文献：
  名称：

  Stereoselective aldol reactions using ticl4 as stereochemical template

  摘要：

  DOI：

  10.1016/s0040-4039(00)89311-9

文献信息

• Synthesis of Stereotriads by Oxymercuration of Substituted Cyclopropylcarbinols
  作者：Janine Cossy、Nicolas Blanchard、Christophe Meyer

  DOI：10.1021/ol0162365

  日期：2001.8.9

  Cyclopropylcarbinol derivatives bearing an adjacent methyl-substituted stereocenter and a remote beta-hydroxy group protected as a pivalate underwent anchimerically assisted regio- and diastereoselective oxymercurations, affording after reductive demercuration, an access to stereotriads.

  [结构：见正文]带有相邻甲基取代的立体中心和被保护为新戊酸酯的远端β-羟基的环丙基甲醇衍生物进行了手性辅助的区域和非对映选择性的氧化汞反应，在还原脱汞后可得到立体三单元。
• Ester derived titanium enolate aldol reaction: chelation controlled diastereoselective synthesis of syn -aldols
  作者：Arun K Ghosh、Jae-Hun Kim

  DOI：10.1016/s0040-4039(00)02227-9

  日期：2001.2

  A chelation controlled and highly diastereoselective synthesis of syn-aldols is described. Aldol reaction of commercially available l-phenylalaninol derived esters with a variety of bidentate oxyaldehydes proceeded with excellent syn-diastereoselectivities and isolated yields.

  描述了螯合受控且高度非对映选择性的合成顺式醇缩醛。可商购的1-苯丙的醛醇缩合反应衍生的酯与多种具有优良的二齿进行的oxyaldehydes顺-diastereoselectivities和分离收率。
• Lewis acid mediated aldol condensations using thioester silyl ketene acetals
  作者：Cesare Gennari、M. Grazia Beretta、Anna Bernardi、Giorgio Moro、Carlo Scolastico、Roberto Todeschini

  DOI：10.1016/s0040-4020(01)87496-2

  日期：1986.1

  silylketene acetal additions to aldehydes are stereoconvergent and give high anti-syn ratios and good chemical yields. An acyclic transition state model was hypothesized in order to account for the observed selectivity. Theoretical methods (MNDO) were used to evaluate the ground-state conformations of thioester silylketene acetals and to model the acyclic transition states. Lewis acid mediated additions

  BF 3 -OEt 2介导的硫酯甲硅烷基乙烯酮缩醛在醛类中的加成反应是立体收敛的，并具有较高的反合成比和良好的化学收率。为了解释观察到的选择性，假设了一个无环过渡态模型。理论方法（MNDO）用于评估硫酯甲硅烷基乙烯酮缩醛的基态构象，并模拟无环过渡态。路易斯酸介导的硫代酸酯甲硅烷基乙烯酮缩醛向2-苯基丙醛（BF 3 -OEt 2），O-苄基乳酸醛（SnCl 4），2,3-0，O-二苄基甘油醛（SnCl 4）和3-的加成反应苄氧基-2-甲基丙醛（TiCl 4）被发现具有高度非对映体选择性，因此可以建立三个连续的立体中心。对于α-，β-或α，β-烷氧基醛，相对立体选择（螯合）可有效控制内部立体选择。使用分子力学（MM2）研究了手性醛的基态构象。
• Synthesis of polypropionate subunits from cyclopropanes
  作者：Magali Defosseux、Nicolas Blanchard、Christophe Meyer、Janine Cossy

  DOI：10.1016/j.tet.2005.05.099

  日期：2005.8

  The oxymercuration-reductive demercuration of several cyclopropanealkanol or their derivatives bearing adjacent stereocenters has been investigated in order to synthesize polypropionate subunits. The crucial importance of the ester protecting group for the remote oxygenated moieties on the mechanism and the stereochemical outcome of these reactions has been rationalized. (c) 2005 Elsevier Ltd. All rights reserved.
• Titanium chloride-mediated reactions of the silyl ketene acetals derived from N-methylephedrine esters: an asymmetric variant of the Mukaiyama reaction
  作者：Cesare Gennari、Lino Colombo、Giorgio Bertolini、Giuliana Schimperna

  DOI：10.1021/jo00389a021

  日期：1987.6