(S)-3-(2,4-dimethoxyphenyl)-2-(4-methoxyphenyl)propan-1-ol | 1057663-19-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (S)-3-(2,4-dimethoxyphenyl)-2-(4-methoxyphenyl)propan-1-ol
• 英文别名: (2S)-3-(2,4-dimethoxyphenyl)-2-(4-methoxyphenyl)propan-1-ol
• CAS: 1057663-19-0
• 化学式: C₁₈H₂₂O₄
• 分子量: 302.37
• InChiKey: FIMQBYBGFXHZBO-OAHLLOKOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.03
• 重原子数：
  22.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  47.92
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (S)-3-(2,4-dimethoxyphenyl)-2-(4-methoxyphenyl)propan-1-ol 在 四溴化碳 、 三溴化硼 、 potassium carbonate 、 三苯基膦 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 30.0h， 生成 雌马酚
  参考文献：
  名称：

  Enantioselective iridium-catalyzed hydrogenation of α-arylcinnamic acids and synthesis of (S)-equol

  摘要：

  By using iridium catalyst based on chiral spiro phosphine-oxazoline ligands, the hydrogenation of alpha-arylcinnamic acids was accomplished under ambient pressure and low catalyst loading (as low as 0.01 mol %), providing useful 2,3-diarylpropionic acids in high yields with excellent enantioselectivities (up to 99% ee). A catalytic enantioselective synthesis of (S)-equol with the present hydrogenation reaction as a key step was accomplished starting from commercially available starting materials in six steps with 48.4% overall yield. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.03.118
• 作为产物：
  描述：

  (E)-3-(2,4-dimethoxyphenyl)-2-(4-methoxyphenyl)acrylic acid 在 lithium aluminium tetrahydride 、 C₅₆H₇₂IrNOP 、 氢气 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 70.0 ℃ 、1.22 MPa 条件下， 反应 74.25h， 生成 (S)-3-(2,4-dimethoxyphenyl)-2-(4-methoxyphenyl)propan-1-ol
  参考文献：
  名称：

  Enantioselective iridium-catalyzed hydrogenation of α-arylcinnamic acids and synthesis of (S)-equol

  摘要：

  By using iridium catalyst based on chiral spiro phosphine-oxazoline ligands, the hydrogenation of alpha-arylcinnamic acids was accomplished under ambient pressure and low catalyst loading (as low as 0.01 mol %), providing useful 2,3-diarylpropionic acids in high yields with excellent enantioselectivities (up to 99% ee). A catalytic enantioselective synthesis of (S)-equol with the present hydrogenation reaction as a key step was accomplished starting from commercially available starting materials in six steps with 48.4% overall yield. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.03.118

文献信息

• Synthetic access to optically active isoflavans by using allylic substitution
  作者：Yuji Takashima、Yuki Kaneko、Yuichi Kobayashi

  DOI：10.1016/j.tet.2009.10.116

  日期：2010.1

  A general approach to the (S)- and (R)-isoflavans was invented, and efficiency of the method was demonstrated by the synthesis of (S)-equol ((S)-3), (R)-sativan ((R)-4), and (R)-vestitol ((R)-5). The key step is the allylic substitution of (S)-6a (Ar1=2,4-(MeO)2C6H3) and (R)-6b (Ar1=2,4-(BnO)2C6H3) with copper reagents derived from CuBr·Me2S and Ar2-MgBr (7a, Ar2=4-MeOC6H4; 7b, 2,4-(MeO)2C6H3; 7c,

  发明了（S）-和（R）-异黄酮的通用方法，并且该方法的效率通过合成（S）-雌马酚（（S）-3），（R）-sativan（（R）-4），和（R）-vestitol（（R）-5）。关键的步骤是（的烯丙基取代小号） - 6a中（AR 1 = 2,4-（MEO）2 C ^ 6 ħ 3）和（- [R ）-图6b（AR 1 = 2,4-（BNO）2 Ç6 H 3）和衍生自CuBr·Me 2 S和Ar 2 -MgBr（7a，Ar 2 = 4-MEOC 6 H 4 ; 7b，2,4-（MEO）2 C 6 H 3 ; 7c，2的铜试剂-momo -4- MEOC 6 ħ 3），家具抗小号ñ 2的产品（[R ）-图8a和（小号） - 8b中，ç93-97％的手性转移，收率为60-75％。产物的烯烃部分被氧化裂解，然后除去Ar 1部分上的Me和Bn基团。最后，用K 2 CO 3和Mitsunobu试剂对溴化苯酚
• A Concise Enantiodivergent Synthesis of Equol
  作者：Shinji Tanimori、Takahito Uemura、Yusuke Saito、Motohiro Sonoda

  DOI：10.1055/a-1303-9935

  日期：2021.4

  Equol, a nonsteroidal estrogen produced from the metabolism of the isoflavonoid phytoestrogen daidzein, has been synthesized as both enantioenriched forms based on MacMillan’s α-arylation of carbonyl compound mediated by amino acid derived indazolidinones and copper precatalysts. The natural form of (S)-equol and its enantiomer (R)-equol have been synthesized in 8 steps from 2,4-dimethoxybenzaldehyde with good enantiomeric purity (90% ee and 90% ee, respectively).

  摘要：从异黄酮类植物雌激素大豆异黄酮代谢产生的非类固醇雌激素Equol，已经合成为根据MacMillan的α-芳基化的酮化合物，通过氨基酸衍生的indazolidinones和铜催化剂来制备富含对映体的形式。自然形式的(S)-equol及其对映体(R)-equol已经从2,4-二甲氧基苯甲醛经过8个步骤合成，其对映纯度良好（分别为90% ee和90% ee）。
• New synthetic route to (S)-(−)-equol through allylic substitution
  作者：Yuji Takashima、Yuichi Kobayashi

  DOI：10.1016/j.tetlet.2008.06.085

  日期：2008.8

  Allylic substitution of allylic picolinate 5 with a copper reagent derived from p-MeOC6H4MgBr (6) and CuBr·Me2S produced the anti SN2′ product 7 with high regioselectivity and efficient chirality transfer. Oxidative cleavage of the olefinic function to the alcohol followed by bromination afforded bromide 16, which upon demethylation and intramolecular ether ring formation furnished (S)-(−)-equol (3)

  用衍生自p -MeOC 6 H 4 MgBr（6）和CuBr·Me 2 S的铜试剂对烯丙基吡啶甲酸5进行烯丙基取代，得到具有高区域选择性和有效手性转移的抗S N 2'产物7。烯烃官能团被氧化裂解为醇，然后溴化，得到溴化物16，该溴化物在脱甲基和形成分子内醚环后提供（S）-（-）-牛尿酚（3）。