(-)-2,3-dihydro-2-(3-methoxyphenyl)-4H-pyran-4-one

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

  反-1-甲氧基-3-(三甲基硅氧基)-1,3-丁二烯 、 3-甲氧基苯甲醛 在 diethylzinc 、 (S)-3,3'-二溴-1,1'-联-2-萘酚 、 三氟乙酸 作用下， 以 正己烷 、 甲苯 为溶剂， 反应 24.5h， 以99%的产率得到(-)-2,3-dihydro-2-(3-methoxyphenyl)-4H-pyran-4-one
  参考文献：
  名称：

  3,3'-Br2-BINOL-Zn络合物：对映选择性杂-Diels-Alder反应的高效催化剂。

  摘要：

  [反应：参见正文]由Et（2）Zn和3,3'-dibromo-1,1'-bi-2-naththol（3,3'-Br（2）-BINOL原位制备的BINOLate-锌复合物）被发现是Danishefsky's二烯和醛对映选择性杂Diels-Alder反应的高效催化剂，可得到定量最高收率和98％ee的2-取代的2,3-二氢-4H-吡喃-4-酮。

  DOI：

  10.1021/ol027034r

文献信息

• 3,3‘-Br₂-BINOL-Zn Complex:  A Highly Efficient Catalyst for the Enantioselective Hetero-Diels−Alder Reaction
  作者：Haifeng Du、Jiang Long、Jieyu Hu、Xin Li、Kuiling Ding

  DOI：10.1021/ol027034r

  日期：2002.11.1

  [reaction: see text] A BINOLate-zinc complex prepared in situ from Et(2)Zn and 3,3'-dibromo-1,1'-bi-2-naphthol (3,3'-Br(2)-BINOL) was found to be a highly efficient catalyst for the enantioselective hetero-Diels-Alder reaction of Danishefsky's diene and aldehydes to give 2-substituted 2,3-dihydro-4H-pyran-4-one in up to quantitative yield and 98% ee.

  [反应：参见正文]由Et（2）Zn和3,3'-dibromo-1,1'-bi-2-naththol（3,3'-Br（2）-BINOL原位制备的BINOLate-锌复合物）被发现是Danishefsky's二烯和醛对映选择性杂Diels-Alder反应的高效催化剂，可得到定量最高收率和98％ee的2-取代的2,3-二氢-4H-吡喃-4-酮。
• Axially Chiral Biaryl Diols Catalyze Highly Enantioselective Hetero-Diels−Alder Reactions through Hydrogen Bonding
  作者：Aditya K. Unni、Norito Takenaka、Hisashi Yamamoto、Viresh H. Rawal

  DOI：10.1021/ja044076x

  日期：2005.2.1

  Axially chiral 1,1'-biaryl-2,2'-dimethanol (3, BAMOL) family of diols are highly effective catalysts for enantioselective hetero-Diels-Alder reactions between aminosiloxydiene 1 and a wide variety of unactivated aldehydes. The reactions proceed in useful yields and excellent enantioselectivities. The diols function in the same capacity as Lewis acids, by activating the aldehyde carbonyl group through

  轴向手性 1,1'-联芳基-2,2'-二甲醇 (3, BAMOL) 二醇家族是氨基甲硅烷氧基二烯 1 和多种未活化醛之间的对映选择性杂 Diels-Alder 反应的高效催化剂。反应以有用的产率和优异的对映选择性进行。二醇的功能与路易斯酸相同，通过氢键活化醛羰基。
• 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.
• Discovery of Exceptionally Efficient Catalysts for Solvent-Free Enantioselective Hetero-Diels−Alder Reaction
  作者：Jiang Long、Jieyu Hu、Xiaoqiang Shen、Baoming Ji、Kuiling Ding

  DOI：10.1021/ja0172518

  日期：2002.1.1

  Combinatorial coordination chemistry strategy combined with high-throughput screening techniques has been successfully applied to engineering practical enantioselective catalysts for asymmetric hetero-Diels-Alder reaction. The reaction of Danishefsky's diene with a variety of aldehydes can be carried out with 0.1-0.005 mol % of H4-BINOL/Ti/H4-BINOL or H4-BINOL/Ti/H8-BINOL catalysts at room temperature under solvent- and MS-free conditions to afford dihydropyrone derivatives with up to quantitative yield and 99.8% ee.