(R)-3-[1,3]Dioxan-2-yl-1-phenyl-propan-1-ol | 144178-32-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: (R)-3-[1,3]Dioxan-2-yl-1-phenyl-propan-1-ol
• CAS: 144178-32-5
• 化学式: C₁₃H₁₈O₃
• 分子量: 222.284
• InChiKey: ZOUFBGGLLPYOON-GFCCVEGCSA-N

物化性质

• 沸点：
  352.2±22.0 °C(Predicted)
• 密度：
  1.102±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.26
• 重原子数：
  16.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  38.69
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  甲氧基-三氟甲基苯 、 (R)-3-[1,3]Dioxan-2-yl-1-phenyl-propan-1-ol 在 4-二甲氨基吡啶 作用下， 以 氯仿 为溶剂， 反应 0.5h， 生成 (R)-3,3,3-Trifluoro-2-methoxy-2-phenyl-propionic acid (R)-3-[1,3]dioxan-2-yl-1-phenyl-propyl ester
  参考文献：
  名称：

  Ti-TADDOLate-catalyzed, highly enantioselective addition of alkyl- and aryl-titanum derivatives to aldehydes

  摘要：

  Toluene-ether or toluene-hexane solutions of aryl and alkyl triisopropoxy titanium reagents (free of Li, Mg, or Zn salts) are prepared from the corresponding Li or Grignard reagents and ClTi((OPr)-Pr-i)(3), with careful removal of salts (centrifugation of LiCl or of dioxane.MgX(2), and addition of 12-crown-4). The solutions of the organotitanium compounds are combined with one equiv. of an aldehyde and 0.2 equiv. of (R,R)-diisopropoxy-(alpha,alpha,alpha',alpha'-tetraphenyl-2,2-dimethyl-1,3-dioxolane-4,5-dimethanolato) titanium (Ti-TADDOLate 3) at dry-ice temperature. Warming up to room temperature leads to nucleophilic addition to the (Si)-face of the aldehydes with enantioselectivities as high as 99.5 : 0.5 (products 4 - 33 in Scheme 4). Functional groups or protecting groups and branching in the Ti-R group and in the aldehyde must be remote from the reacting centers. Aryl groups can be added to aldehydes by this method. - In contrast to all the enantioselective R(2)Zn additions to aldehydes, in which only one R-group is actually transferred, a twice as economic use is made of the originally employed R-metal reagent in the method described here. - A procedure for multigram preparation of the spiro-Ti-TADDOLate (2) employed for the in situ generation of the catalyst (3) is described, and details of the determination of enantiomer ratios (er) by GC and NMR methods are given (Tab. 2, 3). The mechanistic interpretation of Ti-TADDOLate-mediated nucleophilic additions as derived previously (ref.(4e)) is also compatible with this monometallic variant of the method.

  DOI：

  10.1016/s0040-4020(01)90475-2
• 作为产物：
  描述：

  苯甲醛 、 alkaline earth salt of/the/ methylsulfuric acid 在 1,4-二氧六环 、 titanium(IV) isopropylate 、 bis{(4R,5R)-2,2-dimethyl-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanolato-O,O'}titanium(IV) 、 zinc(II) chloride 作用下， 生成 (R)-3-[1,3]Dioxan-2-yl-1-phenyl-propan-1-ol 、 (-)-3-<1,3>dioxan-2-yl-1-phenyl-propan-1-ol
  参考文献：
  名称：

  秒的对映选择性制备。使用亚化学计量的TADDOL-钛酸酯从格氏试剂原位生成的醛和二烷基锌化合物中的乙醇

  摘要：

  使用Schlenk技巧（通过添加1,4-二恶烷，从醚溶液中沉淀出MgX 2），将格氏试剂RMgX（X = Cl，Br，I）和0.5当量的混合物。可以将Et 2 O中的ZnCl 2转化为烷基锌R 2 Zn，然后在Ti（OCHMe 2）4和手性钛酸酯的存在下，将脂族和芳族醛的对映选择性高达99：1。由α，α，α'，α'-四芳基-1,3-二氧戊环-4,5-二甲醇（TADDOL）制得。格氏试剂盒也可以使用双键，苯环或缩醛基。比较了不同的TADDOL在这类对映选择性反应中的用途。

  DOI：

  10.1016/0040-4020(92)80023-9