(E)-ethyl 2-diazohex-3-enoate | 187950-49-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-ethyl 2-diazohex-3-enoate
• 英文别名: ethyl (E)-2-diazohex-3-enoate
• CAS: 187950-49-8
• 化学式: C₈H₁₂N₂O₂
• 分子量: 168.195
• InChiKey: OGTLEDQAIJDANE-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  二甲基苯基硅烷 、 (E)-ethyl 2-diazohex-3-enoate 在 dirhodium tetraacetate 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 以65%的产率得到(E)-2-(Dimethyl-phenyl-silanyl)-hex-3-enoic acid ethyl ester
  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：

  反式-3-己烯酸 在 ABSA 、 硫酸 、 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 3.5h， 生成 (E)-ethyl 2-diazohex-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

文献信息

• 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。
• Gold-Catalyzed C–H Bond Functionalization of Metallocenes: Synthesis of Densely Functionalized Ferrocene Derivatives
  作者：Enol López、Giacomo Lonzi、Luis A. López

  DOI：10.1021/om500638t

  日期：2014.11.10

  A convenient process for the direct functionalization of ferrocene that exploits the high electrophilic character of gold–vinyl carbenoids catalytically generated from vinyldiazo compounds and gold complexes is reported. This process takes place with complete regioselectivity (vinilogous reactivity). The synthesis of the corresponding ruthenocene analogues has also been achieved. Preliminary studies

  据报道，有一种方便的二茂铁直接官能化方法，该方法利用了从乙烯基重氮化合物和金络合物催化生成的金-乙烯基类胡萝卜素的高亲电特性。该过程以完全的区域选择性（葡萄酒反应性）进行。相应的钌茂茂类似物的合成也已经实现。对这些新的有机金属化合物的反应性的初步研究似乎表明，相邻的二茂铁基团的存在赋予易干燥的好氧烯丙基氧化所表现出的官能化碳链特定的反应性。