4-(methoxycarbonyl)-5-methyl-5-phenyl-2-oxazoline | 189825-83-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 4-(methoxycarbonyl)-5-methyl-5-phenyl-2-oxazoline
• 英文别名: methyl (4S,5R)-5-methyl-5-phenyl-4H-1,3-oxazole-4-carboxylate
• CAS: 189825-83-0
• 化学式: C₁₂H₁₃NO₃
• 分子量: 219.24
• InChiKey: YXYRHTUQQGAGNE-ZYHUDNBSSA-N

物化性质

• 沸点：
  305.9±52.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  异腈基乙酸甲酯 、 苯乙酮 在 三乙胺 、 copper(l) chloride 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 24.0h， 以54%的产率得到4-(methoxycarbonyl)-5-methyl-5-phenyl-2-oxazoline
  参考文献：
  名称：

  银（I）/三乙胺催化氟烷基芳基酮与异氰基乙酸甲酯的高度非对映选择性醛醇缩合反应

  摘要：

  发现芳基氟代烷基酮与异氰基乙酸甲酯的过渡金属催化的羟醛反应以高的非对映选择性进行，这与非氟化酮的类似反应中非常差的非对映选择性形成鲜明对比。公开了AgClO 4 / NEt 3作为均相催化剂（1摩尔％）对于这些反应的优越性。

  DOI：

  10.1016/s0040-4039(00)79964-3

文献信息

• Enantioselective synthesis of chiral oxazolines from unactivated ketones and isocyanoacetate esters by synergistic silver/organocatalysis
  作者：Pablo Martínez-Pardo、Gonzalo Blay、M. Carmen Muñoz、José R. Pedro、Amparo Sanz-Marco、Carlos Vila

  DOI：10.1039/c8cc00856f

  日期：——

  acid has been applied in the reaction of unactivated ketones with tert-butyl isocyanoacetate to give chiral oxazolines bearing a quaternary stereocenter. The formal [3+2] cycloaddition provided high yields of the corresponding cis-oxazolines with good diastereoselectivity and excellent enantioselectivity, being applied to aryl–alkyl and alkyl–alkyl ketones.

  结合了双功能布朗斯台德碱-方酰胺有机催化剂和Ag +的路易斯酸的多催化方法已用于未活化的酮与异氰基乙酸叔丁酯的反应中，得到具有季立体中心的手性恶唑啉。正式的[3 + 2]环加成反应提供了高产率的相应的顺-恶唑啉，具有良好的非对映选择性和出色的对映选择性，可用于芳基-烷基和烷基-烷基酮。
• Highly Active Copper-Network Catalyst for the Direct Aldol Reaction
  作者：Hidetoshi Ohta、Yasuhiro Uozumi、Yoichi M. A. Yamada

  DOI：10.1002/asia.201100284

  日期：2011.9.5

  The development of a highly active solid‐phase catechol–copper network catalyst for direct aldol reaction is described. The catalyst was prepared from an alkyl‐chain‐linked bis(catechol) and a copper(II) complex. The direct aldol reaction between carbonyl compounds (aldehydes and ketones) and methyl isocyanoacetate was carried out using 0.1–1 mol % [Cu] catalyst to give the corresponding oxazolines

  描述了用于直接醛醇缩合反应的高活性固相邻苯二酚-铜网络催化剂的开发。该催化剂由烷基链连接的双（邻苯二酚）和铜（II）配合物制得。羰基化合物（醛和酮）与异氰基乙酸甲酯之间的直接羟醛反应是使用0.1–1 mol％[Cu]催化剂进行的，生成相应的恶唑啉，收率高达99％，反式/顺式比> 99： 1。催化剂可以重复使用而不会失去催化活性。还描述了合理的反应途径。
• Transition Metal/Base-Catalyzed Aldol Reactions of Isocyanoacetic Acid Derivatives with Prochiral Ketones, a Straightforward Approach to Stereochemically Defined β,β-Disubstituted-β-hydroxy-α-amino Acids.¹ Scope and Limitations
  作者：Vadim A. Soloshonok、Alexey D. Kacharov、Dimitry V. Avilov、Kohki Ishikawa、Nobuya Nagashima、Tamio Hayashi

  DOI：10.1021/jo9623402

  日期：1997.5.1

  A systematic study of the transition metal/base-catalyzed aldol reactions of methyl isocyanoacetate with a wide range of prochiral ketones, giving rise to the 4-(methoxycarbonyl)-5,5-disubstituted-2-oxazolines, has been made. The diastereoselectivity of these reactions was found to be influenced by a mix of several factors, including steric characteristic of the substituents, nature of the catalyst, electrostatic, and electron donor-acceptor type interactions. The former factor, a stereochemical discrimination between the substituents at the ketone carbon, was shown to be the most pronounced in controlling of the stereochemical outcome, which could be markedly improved with a proper choice of the catalyst. In particular, for the reactions of methyl isocyanoacetate with polyhaloalkyl aryl(alkyl) ketones, high diastereoselectivity (80-98% de) was achieved, thus allowing for straightforward and generalized access to the corresponding (2R*,3R*)-beta,beta-disubstituted-beta-hydroxy-alpha-amino carboxylic acid.