ethyl (E)-2-diazo-4-phenylbut-3-enoate | 126580-12-9

• 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: ethyl (E)-2-diazo-4-phenylbut-3-enoate
• 英文别名: (E)-ethyl 2-diazo-4-phenylbut-3-enoate
• CAS: 126580-12-9
• 化学式: C₁₂H₁₂N₂O₂
• 分子量: 216.239
• InChiKey: DZSZMIRMGOGNPX-CMDGGOBGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  28.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl (E)-2-diazo-4-phenylbut-3-enoate 在 dirhodium tetraacetate 、 水 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以77%的产率得到rac-(E)-ethyl 2-hydroxy-4-phenylbut-3-enoate
  参考文献：
  名称：

  A Stereospecific Access to Allylic Systems Using Rhodium(II)−Vinyl Carbenoid Insertion into Si−H, O−H, and N−H Bonds

  摘要：

  Rhodium-catalyzed decomposition of alpha-vinyldiazoesters in the presence of silanes, alcohols, ethers, amines, and thiols have been shown to produce the corresponding alpha-silyl, alpha-hydroxy, alpha-alkoxy, alpha-amino, and alpha-thioalkoxy esters in generally good yield with a complete retention of the stereochemistry of the double bond of the diazo precursor. An extension of the process in homochiral series has also been devised using either a chiral auxiliary attached to the ester function or achiral alpha-vinyldiazoesters and Doyle's chiral catalyst Rh-2(MEPY)(4). In the former approach, pantolactone as chiral auxiliary gave diastereoselectivities of up to 70%, while the second approach produced the desired allylsilane with ee as high as 72%. On the other hand, Rh-2(MEPY)(4)-catalyzed insertion into the O-H bond of water led to poor or no enantioselectivity in good agreement with recent literature reports.

  DOI：

  10.1021/jo961952j
• 作为产物：
  描述：

  4-苯基-3-丁烯酸 在 硫酸 、 4-乙酰氨基苯磺酰叠氮 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 10.08h， 生成 ethyl (E)-2-diazo-4-phenylbut-3-enoate
  参考文献：
  名称：

  铑 (II) 催化的炔基卡宾插入 N–H 键

  摘要：

  首次在 Rh 催化下将炔基卡宾插入 N-H 键。炔基腙羧酸盐用作供体-受体卡宾前体，并巧妙地插入各种胺、酰胺和 1,2-二胺的 N-H 键中。以良好至优异的产率获得了多种3-炔基3,4-二氢喹喔啉-2(1 H )-酮和密集官能化的α-炔基α-氨基酯。此外，还展示了化学选择性 N-H 插入反应、机理研究以及用于获得有价值的杂环的各种合成转化。

  DOI：

  10.1021/acs.orglett.4c01345

文献信息

• Synthesis of Pyridines by Carbenoid-Mediated Ring Opening of 2<i>H</i>-Azirines
  作者：Nicole S. Y. Loy、Alok Singh、Xianxiu Xu、Cheol-Min Park

  DOI：10.1002/anie.201209301

  日期：2013.2.18

  a wide range of substituents on the resulting pyridine ring using mild reaction conditions (see scheme; esp=α,α,α′,α′‐tetramethyl‐1,3‐benzenedipropionic acid). The formation of the key intermediate is catalyst‐controlled, and subsequent cyclization and oxidation affords pyridines in excellent yields. The method has been used for the efficient synthesis of polyarylpyridines.

  漫游范围：使用温和的反应条件（参见方案； esp =α，α，α'，α'-四甲基-1,3-苯二丙酸），标题反应可耐受吡啶环上的大量取代基。关键中间体的形成受催化剂控制，随后的环化和氧化反应使吡啶具有优异的收率。该方法已用于有效合成聚芳基吡啶。
• Chemodivergent Synthesis of Oxazoles and Oxime Ethers Initiated by Selective C–N/C–O Formation of Oximes and Diazo Esters
  作者：Zhenjie Qi、Shaozhong Wang

  DOI：10.1021/acs.orglett.1c03252

  日期：2021.11.5

  Chemodivergent reactions of oximes and diazo esters involving Rh-catalyzed [3+2] annulation and photodriven O–H insertion have been developed to generate oxazoles and oxime ethers. A range of aldehyde and ketone oximes reacted with α-diazocarbonyl compounds in a controllable manner in which functional groups, including ketone, ester, amide, ether, thiol ether, silane, alkene, allene, and alkyne groups

  已经开发了涉及 Rh 催化的 [3+2] 环化和光驱动 O-H 插入的肟和重氮酯的化学发散反应，以生成恶唑和肟醚。一系列醛和酮肟以可控方式与 α-重氮羰基化合物反应，其中包括酮、酯、酰胺、醚、硫醇醚、硅烷、烯烃、丙二烯和炔基在内的官能团具有良好的耐受性。
• Asymmetric Cyclopropanations by Rhodium(II) <i>N</i>-(Arylsulfonyl)prolinate Catalyzed Decomposition of Vinyldiazomethanes in the Presence of Alkenes. Practical Enantioselective Synthesis of the Four Stereoisomers of 2-Phenylcyclopropan-1-amino Acid
  作者：Huw M. L. Davies、Paul R. Bruzinski、Debra H. Lake、Norman Kong、Michael J. Fall

  DOI：10.1021/ja9604931

  日期：1996.1.1

  to]dirhodium. The carbenoid structure has a critical effect on the degree of asymmetric induction, and the combination of a small electron-withdrawing group such as a methyl ester and an electron-donating group such as vinyl or phenyl resulted in the highest levels of enantioselectivity. The use of electron neutral alkenes and pentane as solvent also enhanced the enantioselectivity of the process.

  N-(芳基磺酰基)脯氨酸铑在烯烃存在下催化乙烯基重氮甲烷的分解导致以高度非对映选择性和对映选择性模式合成官能化环丙烷的非常通用的方法。进行了详细研究以确定控制该过程的对映选择性的关键因素。使用环状 N-(芳基磺酰基)氨基酸作为二铑催化剂的配体获得了最高水平的对映选择性，优化的催化剂是四[N-[(4-十二烷基苯基)磺酰基]-(L)-脯氨酰]二铑。卡宾结构对不对称诱导的程度有关键影响，小的吸电子基团（例如甲酯）和给电子基团（例如乙烯基或苯基）的组合导致最高水平的对映选择性。使用电子中性烯烃和戊烷作为溶剂也提高了该过程的对映选择性。这种化学的合成效用...
• Gold-Catalyzed Formal [3 + 3] and [4 + 2] Cycloaddition Reactions of Nitrosobenzenes with Alkenylgold Carbenoids
  作者：Vinayak Vishnu Pagar、Appaso Mahadev Jadhav、Rai-Shung Liu

  DOI：10.1021/ja209980d

  日期：2011.12.28

  We report two new formal cycloaddition reactions between nitrosobenzenes and alkenylgold carbenoids. We obtained quinoline oxides 3 in satisfactory yields from the gold-catalyzed [3 + 3]-cycloadditions between nitrosobenzenes and alkenyldiazo esters 1. For propargyl esters 5, its resulting gold carbenes react with nitrosobenzene to give alkenylimine 8, followed by a [4 + 2]-cycloaddition with nitrosobenzene

  我们报告了亚硝基苯和链烯基金类卡宾之间的两种新的正式环加成反应。我们从亚硝基苯和烯基重氮酯 1 之间的金催化 [3 + 3]-环加成反应中以令人满意的收率获得了喹啉氧化物 3。对于炔丙酯 5，其产生的金卡宾与亚硝基苯反应得到烯亚胺 8，然后是 [4 + 2]-与亚硝基苯的环加成。
• The Phenylthiocyclopropylsilyl Group: a Useful Latent Hydroxy Group
  作者：Rémy Angelaud、Yannick Landais

  DOI：10.1016/s0040-4020(00)00112-5

  日期：2000.3

  The α-dimethyl(1-phenylthio)cyclopropylsilyl group was used as a new masked hydroxy group. Three procedures have been devised to allow the oxidation of this silicon group in the presence of various functionalities. The desired alcohols are obtained in high yields with retention of configuration at the carbon centre.

  α-二甲基（1-苯硫基）环丙基甲硅烷基被用作新的掩蔽羟基。已经设计了三种方法以允许在各种官能团存在下该硅基团的氧化。以高收率获得所需的醇，并保持碳中心的构型。