2-(2'-methoxyphenyl)-2,3-dihydro-4H-pyran-4-one | 80127-44-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-(2'-methoxyphenyl)-2,3-dihydro-4H-pyran-4-one
• 英文别名: 4H-Pyran-4-one, 2,3-dihydro-2-(2-methoxyphenyl)-；2-(2-methoxyphenyl)-2,3-dihydropyran-4-one
• CAS: 80127-44-2
• 化学式: C₁₂H₁₂O₃
• 分子量: 204.225
• InChiKey: USXRDWKUDRMMPX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (E)-5-methoxy-1-(2'-methoxyphenyl)-1-(trimethylsilyloxy)pent-4-en-3-one 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以91%的产率得到2-(2'-methoxyphenyl)-2,3-dihydro-4H-pyran-4-one
  参考文献：
  名称：

  Experiments Directed Towards the Synthesis of Anthracyclinones. XXXIV Hetero-Diels - Alder Reactions Using Chiral Boron and Titanium Reagents

  摘要：

  苯甲醛或邻甲氧基苯甲醛与一系列硅烷氧基二烯通过手性酰氧硼烷（CAB）配合物（4）催化反应，产生高收率的对向异构体产物，而不是杂环Diels-Alder反应。尝试使用蒽醌醛进行类似的催化反应失败，但使用2当量的CAB配合物（1）随后进行环化反应，促进了醛（7）和二烯（12）之间的形式杂环Diels-Alder反应，产生二氢吡喃（24），收率为45％，对2'R对映体有79％的对映选择性。使用手性钛配合物Ti [(R)-BINOL] Cl2，Ti [(R,R)-TADDOL] Cl2和Ti [(R)-BINOL] 2进行了醛（7）和二烯（12）之间的杂环Diels-Alder反应的研究。前两种配合物分别在-30℃和-78℃促进反应，但对映选择性较低。

  DOI：

  10.1071/ch98181

文献信息

• A Lewis Base-catalyzed Hetero Diels–Alder Reaction between Aldehydes and the Danishefsky’s Diene
  作者：Teruaki Mukaiyama、Takayuki Kitazawa、Hidehiko Fujisawa

  DOI：10.1246/cl.2006.328

  日期：2006.3

  A lithium methoxide-catalyzed hetero Diels–Alder reaction of aromatic and aliphatic aldehydes with 1-methoxy-3-trimethylsilyloxy-1,3-butadiene (Danishefsky’s diene) is described. It proceeds through the Mukaiyama-Aldol reaction pathway and affords the corresponding 2,3-dihydropyran-4-one skeletons in good to excellent yields.

  报道了由甲醇锂催化的芳香醛和脂肪醛与1-甲氧基-3-三甲基硅氧基-1,3-丁二烯（Danishefsky双烯）的杂Diels-Alder反应。该反应通过Mukaiyama-Aldol反应途径进行，并以优异的产率获得了相应的2,3-二氢吡喃-4-酮骨架。
• Asymmetric hetero Diels–Alder reaction using chiral cationic metallosalen complexes as catalysts
  作者：Kohsuke Aikawa、Ryo Irie、Tsutomu Katsuki

  DOI：10.1016/s0040-4020(00)01048-6

  日期：2001.1

  –chromium(III) complexes served as the catalysts for asymmetric hetero Diels–Alder reaction of Danishefsky's diene with aldehydes, achieving high enantioselectivity (up to 97% ee at 0°C). The reactions of aldehydes bearing no precoordinating functional group were well effected by using (R,R)-complexes as catalysts, while those of aldehydes bearing a precoordinating functionality were better effected by

  手性阳离子（R，S）-或（R，R）-（salen）–锰（III）和–铬（III）配合物用作Danishefsky's二烯与醛的不对称杂Diels–Alder反应的催化剂，实现了高对映选择性（0°C时ee高达97％）。通过使用（R，R）络合物作为催化剂，不带有预配位官能团的醛的反应效果良好，而通过使用（R，S）络合物，带有预配位官能团的醛的反应效果更好。
• Chromium-Thiophene-salen-Based Polymers for Heterogeneous Asymmetric Hetero-Diels–Alder Reactions
  作者：Anaïs Zulauf、Mohamed Mellah、Régis Guillot、Emmanuelle Schulz

  DOI：10.1002/ejoc.200701218

  日期：2008.4

  proved to beefficient catalysts for promoting asymmetric hetero-Diels–Alder reactions with good activities and high enantioselectivities (up to 88 % ee). These complexes were successfully electropolymerized to give chiral polymers as insoluble powders for use in asymmetric heterogeneous catalysis. When engaged in successive hetero-Diels–Alder reactions, they afforded the expected products in high yield

  已经合成了新的手性噻吩-salen 配体，并且相应的铬配合物被证明是促进不对称杂 Diels-Alder 反应的有效催化剂，具有良好的活性和高对映选择性（高达 88% ee）。这些配合物被成功地电聚合得到手性聚合物，作为不溶性粉末用于不对称多相催化。当进行连续的异-Diels-Alder 反应时，他们以高产率和对映选择性提供了预期的产物，在长达 15 次循环中没有效率损失。手性铬-salen-噻吩聚合物也成功地用于多底物程序，在该程序中，每次重复使用时都会引入结构不同的新醛，以提供纯形式的所需吡喃酮。(© Wiley-VCH Verlag GmbH & Co. KGaA,
• Dramatically Synergetic Effect of Carboxylic Acid Additive on Tridentate Titanium Catalyzed Enantioselective Hetero-Diels–Alder Reaction: Additive Acceleration and Nonlinear Effect
  作者：Yu Yuan、Jiang Long、Jie Sun、Kuiling Ding

  DOI：10.1002/1521-3765(20021104)8:21<5033::aid-chem5033>3.0.co;2-t

  日期：2002.11.4

  This paper describes the successful development of a group of highly, efficient chiral tridentate titanium catalysts for hetero-Diels - Alder reaction of Danishefsky's diene and a variety of aldehydes through ligand and additive diversity. Dramatically synergetic effect of carboxylic acid additives and influence of substituent in chiral Schiff base ligands on the enantioselectivities of the reaction are reported. It was found that a chiral drug Naproxen (A21) was a highly efficient additive for Ti-catalyzed HDA reaction, affording 2-substituted 2,3-dihydro-4H-pyran-4-one in up to 97% ee and > 99% yields. Quantitative study of the effect of chiral carboxylic acid A21 revealed that the reaction could be accelerated by one order of magnitude. Another interesting feature of present catalytic system is the existence of significant positive nonlinear effect. which indicates that the heterochiral Schiff base-titanium complexes may have higher stability than their homochiral counterparts. As a result. the homochiral Schiff base - titanium complexes with higher ee than that of starting ligand will react with carboxylic acid additive to form the more active species and predominate the catalytic process. The isolation and characterization of stable heterochiral ((+/-)-L1)(2)Ti complex has also been successful, which strongly supported the explanation for positive nonlinear effect observed in the catalytic system.
• Hetero Diels-Alder Type Reactions Between Danishefsky’s Dienes in the Presence of Lewis Base Catalysts. An Efficient Method for the Synthesis of Substituted 2,3-Dihydropyran-4-ones
  作者：Teruaki Mukaiyama、Takayuki Kitazawa

  DOI：10.3987/com-06-s(o)52

  日期：——