(E)-3-phenylbut-2-en-1-yl 3-oxobutanoate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-3-phenylbut-2-en-1-yl 3-oxobutanoate
• 英文别名: [(E)-3-phenylbut-2-enyl] 3-oxobutanoate
• 化学式: C₁₄H₁₆O₃
• 分子量: 232.279
• InChiKey: XKVPRHMOPHEDEQ-DHZHZOJOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-3-phenylbut-2-en-1-yl 3-oxobutanoate 在 sodium hydroxide 、 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以 乙腈 为溶剂， 反应 6.0h， 生成 trans-3-phenyl-3-methyl-2-propen-1-yl diazoacetate
  参考文献：
  名称：

  Asymmetric intramolecular cyclopropanation of diazo compounds with metallosalen complexes as catalyst: structural tuning of salen ligand

  摘要：

  Intramolecular cyclopropanation of alkenyl alpha-diazoacetates and alkenyl diazomethyl ketones was examined by using optically active (ON+)Ru(11)(salen) and Co(II)(salen) complexes as catalysts. For the cyclization of 2-alkenyl alpha-diazoacetates, Co(II)(salen) complexes 9 and 10 were found to be superior catalysts to the corresponding (ON+)Ru(11)(salen) complexes 4 and 5. On the other hand, (ON+)Ru(II)(salen) complex 2 was found to be the catalyst of choice for the cyclization of 3-alkenyl diazomethyl ketones, and complex 4 was found to be a good catalyst for the cyclization of (E)-4-alkenyl diazomethyl ketones. The present study demonstrates that metallosalen complexes, especially optically active (ON+)Ru(II)(salen) and Co(11)(salen) complexes, can serve as efficient catalysts for the cyclization of alkenyl diazocarbonyl compounds, if a suitable salen ligand is used as the chiral auxiliary. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00167-8
• 作为产物：
  描述：

  双乙烯酮 、 (E)-3-phenylbut-2-en-1-ol 在 4-二甲氨基吡啶 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以92%的产率得到(E)-3-phenylbut-2-en-1-yl 3-oxobutanoate
  参考文献：
  名称：

  CpRu II-手性双am配合物催化β-酮烯丙基酯的不对称卡罗尔型脱羧烯丙基化

  摘要：

  报道了β-酮烯丙基酯与带有手性双am型二齿配体的阳离子CpRu配合物的卡洛尔重排型分子内脱羧烯丙基化。该催化体系允许将β-酮酸的单取代的3-芳基烯丙基酯有效地转化为相应的γ，δ-烯酮。明显地，催化转化率比先前报道的实例的催化转化率高一个数量级。发达的反应系统显示出改进的区域选择性和对映选择性以及广泛的底物范围。使用NMR实验的机理研究，底物结构/反应性关系研究和交叉实验揭示了可能的反应途径，其中涉及β-酮酸的烯醇化物。

  DOI：

  10.1016/j.tet.2019.130888

文献信息

• Synthesis of B-keto esters
  申请人：——

  公开号：US20020102671A1

  公开（公告）日：2002-08-01

  &bgr;-keto esters are prepared by way of a lipase-catalyzed transesterification. The synthetic methodology provides a simple scheme for the synthesis of optically active &bgr;-keto esters that are useful building blocks and starting materials for natural product synthesis. Moreover, the methodology employs mild, solvent-free conditions. The methodology may also be employed for resolving racemic alcohols.

  &bgr;-酮酯是通过脂肪酶催化的酯交换反应制备的。该合成方法为合成具有光学活性的&bgr;-酮酯提供了一个简单的方案，而&bgr;-酮酯是天然产物合成的有用构件和起始材料。此外，该方法采用温和、无溶剂的条件。该方法还可用于解决外消旋醇的问题。
• US6642035B2
  申请人：——

  公开号：US6642035B2

  公开（公告）日：2003-11-04
• Asymmetric intramolecular cyclopropanation of diazo compounds with metallosalen complexes as catalyst: structural tuning of salen ligand
  作者：Biswajit Saha、Tatsuya Uchida、Tsutomu Katsuki

  DOI：10.1016/s0957-4166(03)00167-8

  日期：2003.4

  Intramolecular cyclopropanation of alkenyl alpha-diazoacetates and alkenyl diazomethyl ketones was examined by using optically active (ON+)Ru(11)(salen) and Co(II)(salen) complexes as catalysts. For the cyclization of 2-alkenyl alpha-diazoacetates, Co(II)(salen) complexes 9 and 10 were found to be superior catalysts to the corresponding (ON+)Ru(11)(salen) complexes 4 and 5. On the other hand, (ON+)Ru(II)(salen) complex 2 was found to be the catalyst of choice for the cyclization of 3-alkenyl diazomethyl ketones, and complex 4 was found to be a good catalyst for the cyclization of (E)-4-alkenyl diazomethyl ketones. The present study demonstrates that metallosalen complexes, especially optically active (ON+)Ru(II)(salen) and Co(11)(salen) complexes, can serve as efficient catalysts for the cyclization of alkenyl diazocarbonyl compounds, if a suitable salen ligand is used as the chiral auxiliary. (C) 2003 Elsevier Science Ltd. All rights reserved.
• CpRuII-chiral bisamidine complex catalyzed asymmetric Carroll-type decarboxylative allylation of β-keto allyl esters
  作者：Shintarou Ogawa、Kengo Miyata、Sho Kawakami、Shinji Tanaka、Masato Kitamura

  DOI：10.1016/j.tet.2019.130888

  日期：2020.2

  that of the previously reported examples. The developed reaction system displays improved regioselectivity and enantioselectivity and a broad substrate scope. Mechanistic studies using NMR experiments, substrate-structure/reactivity relationship studies, and cross-over experiment reveal a possible reaction pathway involving the enolate of the β-keto acid.

  报道了β-酮烯丙基酯与带有手性双am型二齿配体的阳离子CpRu配合物的卡洛尔重排型分子内脱羧烯丙基化。该催化体系允许将β-酮酸的单取代的3-芳基烯丙基酯有效地转化为相应的γ，δ-烯酮。明显地，催化转化率比先前报道的实例的催化转化率高一个数量级。发达的反应系统显示出改进的区域选择性和对映选择性以及广泛的底物范围。使用NMR实验的机理研究，底物结构/反应性关系研究和交叉实验揭示了可能的反应途径，其中涉及β-酮酸的烯醇化物。