ethyl 3,4-dihydro-4-oxo-2-phenyl-2H-pyran-2-carboxylate | 238737-21-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: ethyl 3,4-dihydro-4-oxo-2-phenyl-2H-pyran-2-carboxylate
• 英文别名: Ethyl 4-oxo-2-phenyl-3H-pyran-2-carboxylate
• CAS: 238737-21-8
• 化学式: C₁₄H₁₄O₄
• 分子量: 246.263
• InChiKey: FDJJFDNWBLFVPV-UHFFFAOYSA-N

物化性质

• 沸点：
  358.1±42.0 °C(Predicted)
• 密度：
  1?+-.0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  苯甲酰甲酸乙酯 、 反-1-甲氧基-3-(三甲基硅氧基)-1,3-丁二烯 在 ytterbium tris<(R)-(-)-1,1'-binaphthyl-2,2'-diyl phosphate> 作用下， 以 二氯甲烷 为溶剂， 反应 11.0h， 以90%的产率得到ethyl 3,4-dihydro-4-oxo-2-phenyl-2H-pyran-2-carboxylate
  参考文献：
  名称：

  Chiral rare earth organophosphates as homogeneous Lewis acid catalysts for the highly enantioselective hetero-Diels–Alder reactions

  摘要：

  Various trivalent rare earth-chiral phosphate complexes [(R)-l-RE, (R)-3-RE, and (R)-4-Ce] were prepared and evaluated as a Lewis acid catalyst for the asymmetric hetero-Diels-Alder reaction of aldehydes with the Danishefsky's diene. Some of them effectively promoted the reaction at room temperature in the presence or absence of achiral additives under homogeneous conditions to afford the corresponding cycloadducts with high ee's (up to 99% ee). During these reactions, remarkably high asymmetric amplifications (positive nonlinear effects) were observed as the first example in the metal ion-chiral ligand 1:3 catalytic system. A scandium catalyst bearing the H-8-BNP ligand, (R)-3-Sc, could be recovered after the reaction and successfully reused for the next round of reactions. In addition, the hetero-Diels-Alder reaction of alpha-keto esters was effectively catalyzed by the ytterbium complex, (R)-l-Yb, without any additives thus producing the asymmetric quaternary carbon in excellent enantioselectivities (up to > 99% ee). (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.06.011

文献信息

• DABCO-Mediated [4+2] Annulation of But-3-yn-2-one and Activated Ketones: Facile Preparation of 2,3-Dihydropyran-4-one
  作者：Zhong Lian、Qian-Yi Zhao、Yin Wei、Min Shi

  DOI：10.1002/ejoc.201200264

  日期：2012.6

  that nitrogen-containing Lewis base mediated [4+2] annulation of but-3-yn-2-one with activated ketones could proceed efficiently to give the corresponding 2,3-dihydropyran-4-ones in moderate to good yields under mild conditions. The substrate scope has been carefully examined. Moreover, a plausible reaction mechanism for the [4+2] annulation of but-3-yn-2-one with activated ketones mediated by DABCO has

  我们发现含氮路易斯碱介导的 but-3-yn-2-one 与活化酮的 [4+2] 环化可以有效地进行，以中等至良好的产率得到相应的 2,3-dihydropyran-4-ones。条件温和。底物范围已经过仔细检查。此外，基于先前的文献和我们自己的研究，已经提出了一种由 DABCO 介导的but-3-yn-2-one 与活化酮的 [4+2] 环化的合理反应机制。
• Binaphthol monophosphoric acid derivative and its use
  申请人：Tosoh Corporation

  公开号：EP1038877A1

  公开（公告）日：2000-09-27

  A binaphthol monophosphoric acid derivative of the following formula (1), (2), (3) or (4): wherein each of R1, R2, R3 and R4 which are independent of one another, is hydrogen, a C1-20 linear or branched alkyl group, a C1-20 linear or branched alkenyl group, a C1-20 linear or branched alkynyl group, a phenyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C1-10 linear or branched alkyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C1-10 linear or branched alkenyl group, a phenyl group having its nucleus substituted at the 1-to 4-carbon atom by a C1-10 linear or branched alkynyl group, a naphthyl group or a C3-8 cycloalkyl group, provided that R1 to R4 are not simultaneously hydrogen, wherein each of R5, R6, R7 and R8 which are independent of one another, is hydrogen, a C1-20 linear or branched alkyl group, a C1-20 linear or branched alkenyl group, a C1-20 linear or branched alkynyl group, a phenyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C1-10 linear or branched alkyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C1-10 linear or branched alkenyl group, a phenyl group having its nucleus substituted at the 1-to 4-carbon atom by a C1-10 linear or branched alkynyl group, a naphthyl group or a C3-8 cycloalkyl group.

  下式(1)、(2)、(3)或(4)的二萘酚单磷酸衍生物： 其中相互独立的 R1、R2、R3 和 R4 各为氢、C1-20 直链或支链烷基、C1-20 直链或支链烯基、C1-20 直链或支链炔基、苯基、其核在 1 至 4 碳原子上被 C1-10 直链或支链烷基取代的苯基、在 1 至 4 碳原子处其核被 C1-10 直链或支链烯基取代的苯基、在 1 至 4 碳原子处其核被 C1-10 直链或支链炔基取代的苯基、萘基或 C3-8 环烷基，条件是 R1 至 R4 不同时为氢、 其中相互独立的 R5、R6、R7 和 R8 各为氢、C1-20 直链或支链烷基、C1-20 直链或支链烯基、C1-20 直链或支链炔基、苯基、其核在 1-4 碳原子上被 C1-10 直链或支链烷基取代的苯基、在 1 至 4 碳原子处其核被 C1-10 直链或支链烯基取代的苯基、在 1 至 4 碳原子处其核被 C1-10 直链或支链炔基取代的苯基、萘基或 C3-8 环烷基。
• Chiral rare earth organophosphates as homogeneous Lewis acid catalysts for the highly enantioselective hetero-Diels–Alder reactions
  作者：Hiroshi Furuno、Tetsuji Hayano、Takeshi Kambara、Yuichi Sugimoto、Takeshi Hanamoto、Yumiko Tanaka、Yong Zhi Jin、Takumi Kagawa、Junji Inanaga

  DOI：10.1016/j.tet.2003.06.011

  日期：2003.12

  Various trivalent rare earth-chiral phosphate complexes [(R)-l-RE, (R)-3-RE, and (R)-4-Ce] were prepared and evaluated as a Lewis acid catalyst for the asymmetric hetero-Diels-Alder reaction of aldehydes with the Danishefsky's diene. Some of them effectively promoted the reaction at room temperature in the presence or absence of achiral additives under homogeneous conditions to afford the corresponding cycloadducts with high ee's (up to 99% ee). During these reactions, remarkably high asymmetric amplifications (positive nonlinear effects) were observed as the first example in the metal ion-chiral ligand 1:3 catalytic system. A scandium catalyst bearing the H-8-BNP ligand, (R)-3-Sc, could be recovered after the reaction and successfully reused for the next round of reactions. In addition, the hetero-Diels-Alder reaction of alpha-keto esters was effectively catalyzed by the ytterbium complex, (R)-l-Yb, without any additives thus producing the asymmetric quaternary carbon in excellent enantioselectivities (up to > 99% ee). (C) 2003 Elsevier Ltd. All rights reserved.
• US6274745B1
  申请人：——

  公开号：US6274745B1

  公开（公告）日：2001-08-14
• Chiral dihydropyranones via hetero Diels–Alder reaction of Danishefsky's diene and α-ketoesters: a high-throughput screening approach
  作者：Christian Wolf、Zaid Fadul、Pili A. Hawes、Emily C. Volpe

  DOI：10.1016/j.tetasy.2004.05.024

  日期：2004.7

  The chiral Lewis acid-catalyzed hetero Diels-Alder reaction between Danishefsky's diene and sterically hindered alpha-ketoesters has been optimized using a validated high-throughput screening method. The yields and enantioselectivities of three chiral dihydropyranones obtained by this multi-substrate one-pot screening approach are in excellent agreement with individual screening results. Employing ethyl benzoylformate, ethyl 3-methyl-2-oxobutyrate, and dihydro-4,4-dimethyl-2,3-furandione in one reaction mixture allowed a fast evaluation of chiral Lewis acid composition, solvent, temperature, catalyst loading, and dienophile concentration. The crude product mixtures were analyzed by HPLC using two chiral stationary phases coupled in series to avoid time-consuming work-up procedures. (C) 2004 Elsevier Ltd. All rights reserved.