(2R) butyl 3,4-dihydro-4-oxo-2H-pyran-2-carboxylate | 190017-86-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (2R) butyl 3,4-dihydro-4-oxo-2H-pyran-2-carboxylate
• 英文别名: n-butyl (R)-4-oxo-3,4-dihydro-2H-pyran-2-carboxylate；2H-Pyran-2-carboxylic acid, 3,4-dihydro-4-oxo-, butyl ester, (2R)-；butyl (2R)-4-oxo-2,3-dihydropyran-2-carboxylate
• CAS: 190017-86-8
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: QTTDTNKAFRMTMH-SECBINFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  乙醛酸正丁酯 在 (S,S)-(Bn-Phebox)RhCl₂(H₂O) 三氟乙酸 作用下， 以 甲苯 为溶剂， 反应 1.0h， 生成 (2R) butyl 3,4-dihydro-4-oxo-2H-pyran-2-carboxylate
  参考文献：
  名称：

  Danishefsky的二烯和乙醛酸酯与手性双（恶唑啉基）苯基铑（III）水配合物的不对称杂Diels-Alder反应及其机理研究

  摘要：

  Danishefsky二烯与乙醛酸酯的不对称杂Diels-Alder反应通过手性（Phebox）RhCl 2（H 2 O）络合物[Phebox = 2,6-双（恶唑啉基）苯基]催化高对映选择性和顺（内）-非对映选择性。通过一致的[4 + 2]机理与乙醛酸酯的两个羰基部分的垂直构象。新合成了二溴化物和二氟化物配合物，发现杂Diels–Alder产物的对映选择性比母体二氯化物配合物略高（Cl：80％ee，Br：82％ee，F：84％ee）。

  DOI：

  10.1016/s0040-4020(00)01049-8

文献信息

• Asymmetric Hetero-Diels–Alder Reaction of Danishefsky’s Dienes with α-Carbonyl Esters Catalyzed by an Indium(III)–PyBox Complex
  作者：Bei Zhao、Teck-Peng Loh

  DOI：10.1021/ol400841s

  日期：2013.6.21

  An efficient catalytic enantioselective hetero-Diels–Alder reaction of Danishefsky’s dienes with α-carbonyl esters using a chiral In(III)–pybox complex has been demonstrated. This protocol offers several advantages, including mild reaction conditions, relatively low catalyst loading, and good to excellent enantioselectivities. Furthermore, the absolute configurations of the new alkynyl-containing products

  已证明使用手性In（III）-pybox配合物可以有效地催化Danishefsky二烯与α-羰基酯的对映选择性杂Diels-Alder反应。该方案具有几个优点，包括温和的反应条件，相对较低的催化剂负载量以及良好的对映选择性。此外，通过CD光谱结合TD-DFT计算确定了新的含炔基产物的绝对构型。
• Asymmetric hetero-Diels–Alder reaction of glyoxylate esters and Danishefsky’s diene catalyzed by chiral bis(oxazoline)–lanthanide complexes
  作者：Changtao Qian、Longcheng Wang

  DOI：10.1016/s0040-4039(00)00144-1

  日期：2000.3

  Asymmetric hetero-Diels–Alder reactions of glyoxylate esters and Danishefsky’s diene catalyzed by various chiral bis(oxazoline)–lanthanide complexes afforded the corresponding aldol adducts, which upon treatment with trifluoroacetic acid, furnished the hetero-Diels–Alder product in up to 77% enantiomeric excess and 73% isolated yield.

  各种手性双（恶唑啉）-镧系元素络合物催化乙醛酸酯和Danishefsky's二烯的不对称杂Diels-Alder反应，得​​到相应的羟醛加合物，用三氟乙酸处理后得到的杂Diels-Alder产物高达77％对映体过量和73％的分离产率。
• Chiral bis-trifluoromethanesulfonylamide as a chiral Brønsted acid catalyst for the asymmetric hetero Diels–Alder reaction with Danishefsky’s diene
  作者：Takayuki Tonoi、Koichi Mikami

  DOI：10.1016/j.tetlet.2005.07.043

  日期：2005.9

  Bis-trifluoromethanesulfonylamide (bis-triflylamide) itself works as an efficient chiral Brønsted acid catalyst for the hetero Diels–Alder reactions between Danishefsky’s diene and glyoxylate or phenylglyoxal presumably through double hydrogen bonding.

  双三氟甲磺酰胺（bis-triflylamide）本身可作为一种有效的手性布朗斯台德酸催化剂，用于Danishefsky的二烯与乙醛酸或苯乙二醛之间的杂Diels-Alder反应，大概是通过双氢键。
• Importance of chiral activators in the asymmetric catalysis of Diels-Alder reactions by chiral titanium(IV) complexes
  作者：Satoru Matsukawa、Koichi Mikami

  DOI：10.1016/s0957-4166(97)00045-1

  日期：1997.3

  Asymmetric activation of chiral titanium(IV) complexes is found to be essential to provide higher levels of enantioselectivity than that attained by enantiopure catalysts in Diels-Alder reactions of the Danishefsky diene and glyoxylate.

  发现手性钛（IV）配合物的不对称活化对于提供比对映纯催化剂在Danishefsky二烯和乙醛酸酯的Diels-Alder反应中获得更高水平的对映选择性至关重要。
• The enantioselective Diels–Alder reaction of 1-methoxybuta-1,3-diene with n-butyl glyoxylate catalyzed by the (salen)Cr(III)Cl and Co(II) complexes
  作者：Piotr Kwiatkowski、Monika Asztemborska、Janusz Jurczak

  DOI：10.1016/j.tetasy.2004.08.002

  日期：2004.10

  Commercially available (salen)Cr(III)Cl 4c and (salen)Co(II) 5a complexes were found to promote [4+2]cycloaddition of 1-methoxybuta-1,3-diene 1 to n-butyl glyoxylate 2, affording 6-substituted 2-methoxy-5,6-dihydro-2H-pyrans 3 in good yield and with enantioselectivites of 70-90% ee. The catalyst 5a was also effective in the reaction of Danishefsky's diene 6, piperylene 8 and 2,3-dimethylbuta-1,3-diene 10 with glyoxylate 2, however enantioselectivities were lower. (C) 2004 Elsevier Ltd. All rights reserved.