1-octyl diazoacetoacetate | 127236-69-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-octyl diazoacetoacetate
• 英文别名: octyl 2-diazo-3-oxobutanoate；(E)-3-diazonio-4-octoxy-4-oxobut-2-en-2-olate
• CAS: 127236-69-5
• 化学式: C₁₂H₂₀N₂O₃
• 分子量: 240.302
• InChiKey: XQZMJEWRWJBAHL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  17
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  45.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-octyl diazoacetoacetate 在 氢氧化钾 作用下， 生成 octyl diazoacetate
  参考文献：
  名称：

  在羧酸铑（II）和铑（II）羧酰胺催化的重氮酯的分子内类胡萝卜素碳氢插入中高选择性合成γ-内酯

  摘要：

  乙酸铑（II）和铑（II）乙酰胺催化的重氮酯分解形成γ-内酯，产率高，区域选择性和非对映选择性高。

  DOI：

  10.1016/s0040-4039(01)93408-2
• 作为产物：
  描述：

  辛醇 在 甲烷磺酰基叠氮化物 作用下， 生成 1-octyl diazoacetoacetate
  参考文献：
  名称：

  在羧酸铑（II）和铑（II）羧酰胺催化的重氮酯的分子内类胡萝卜素碳氢插入中高选择性合成γ-内酯

  摘要：

  乙酸铑（II）和铑（II）乙酰胺催化的重氮酯分解形成γ-内酯，产率高，区域选择性和非对映选择性高。

  DOI：

  10.1016/s0040-4039(01)93408-2

文献信息

• Synthesis of Pyrrolidines and Pyrrolizidines with α-Pseudoquaternary Centers by Copper-Catalyzed Condensation of α-Diazodicarbonyl Compounds and Aryl γ-Lactams
  作者：Sébastien Goudedranche、Céline Besnard、Léo Egger、Jérôme Lacour

  DOI：10.1002/anie.201607574

  日期：2016.10.24

  usually dicarbonyl compounds, in a copper‐catalyzed process to yield functionalized pyrrolidines with α‐pseudoquaternary centers. As 1,2‐acyl or ‐phosphoryl migration is preferred, single regioisomers are obtained. Furthermore, in the presence of a Lewis acid, subsequent Friedel–Crafts reactions yield tricyclic pyrrolizidines in excellent yields (90–96 %) and diastereoselectivities (up to >20:1).

  N-芳基γ-内酰胺在铜催化的过程中与受体-重氮试剂（通常为二羰基化合物）发生分子间反应，生成具有α-伪四元中心的官能化吡咯烷。由于首选1,2-酰基或-磷酰基迁移，因此获得了单一的区域异构体。此外，在路易斯酸的存在下，随后的Friedel-Crafts反应以极好的收率（90–96％）和非对映选择性（> 20：1）生成三环吡咯并核苷。
• A switch to vinylogous reactivity of vinyl diazo esters for the C–H allylation of benzamides by merging cobalt and photoredox catalysis
  作者：Nandkishor Prakash Khot、Nitish Kumar Deo、Manmohan Kapur

  DOI：10.1039/d2cc05332b

  日期：——

  Herein, a de novo vinylogous reactivity of vinyl diazo esters in the C–H bond allylation of benzamides has been developed by coalescing cobalt and photoredox catalysis via C–H activation/allyl carbene migratory insertion. A close relationship between the high valent cobalt catalyst and the photocatalyst has been found to be crucial for this reactivity. The reaction uses oxygen as the sole oxidant and

  在此，通过C-H 活化/烯丙基卡宾迁移插入聚结钴和光氧化还原催化，开发了乙烯基重氮酯在苯甲酰胺的 C-H 键烯丙基化中的从头插烯反应性。已发现高价钴催化剂和光催化剂之间的密切关系对于这种反应性至关重要。该反应使用氧气作为唯一的氧化剂，并产生良性氮作为唯一的副产品。对于乙烯基重氮酯和苯甲酰胺，该反应显示出良好的底物范围。该协议的实用性通过几个生物活性分子的后期功能化得到证明。
• A three component 1,3-difunctionalization of vinyl diazo esters enabled by a cobalt catalyzed C–H activation/carbene migratory insertion
  作者：Nandkishor Prakash Khot、Prajyot Jayadev Nagtilak、Nitish Kumar Deo、Manmohan Kapur

  DOI：10.1039/d3cc00295k

  日期：——

  We report herein, a modular, regioselective 1,3-oxyarylation of vinyl diazo esters via a Co-catalyzed C–H activation/carbene migratory insertion cascade. The transformation involves the formation of C–C and C–O bonds in a one-pot fashion and displays a broad substrate scope with respect to both, vinyl diazo esters as well as benzamides. The coupled products were subjected to hydrogenation to access

  我们在此报告了通过共催化的 C-H 活化/卡宾迁移插入级联对乙烯基重氮酯进行模块化、区域选择性 1,3-氧芳基化。这种转化涉及以一锅法形成 C-C 和 C-O 键，并显示出与乙烯基重氮酯和苯甲酰胺有关的广泛底物范围。对偶联产物进行氢化以获得难以捉摸的烯丙醇支架。机理研究揭示了对转化模式的有趣见解，包括 C-H 活化、重氮化合物的卡宾迁移插入以及随后的自由基加成作为转化的关键步骤。
• Electronic and steric control in carbon-hydrogen insertion reactions of diazoacetoacetates catalyzed by dirhodium(II) carboxylates and carboxamides
  作者：Michael P. Doyle、Larry J. Westrum、Wendelmoed N. E. Wolthuis、Marjorie M. See、William P. Boone、Vahid Bagheri、Matthew M. Pearson

  DOI：10.1021/ja00056a021

  日期：1993.2

  Carboxylate and carboxamide ligands on dirhodium(II) catalysts can provide enormous regiocontrol in carbon-hydrogen insertion reactions of diazoacetate esters. Whereas 2,3,4-trimethyl-3-pentyl diazoacetoacetate (1) forms gamma-lactone products from insertion into primary and tertiary C-H bonds in a statistical distribution (61:39) with dirhodium(II) tetrakis(perfluorobutyrate), only tertiary C-H insertion is observed with dirhodium(II) tetraacetamide. Similar results are obtained with 2-methyl-2-octyl diazoacetoacetate (3), where competition for insertion exists between secondary and primary C-H bonds and electronic factors govern regioselection. However, with 2-methyl-3-isopropyl-3-heptyl diazoacetoacetate (2) and 2-methyl-1-phenyl-2-propyl diazoacetoacetate (4), product distributions from C-H insertion are invariant with the dirhodium(II) ligands; insertion into a secondary C-H bond is favored over tertiary C-H insertion with 2 (95:5), and insertion into a primary C-H bond is preferred to benzylic secondary C-H insertion with 4 (70:30). In such cases, which are amenable to analyses by MM2 calculations, regioselectivity is determined by conformational preferences for which C-H insertion selectivity can be as random as that found with 2 and 4. When only one C-H bond site is available for insertion to form a five-membered ring product, only one gamma-lactone is observed from reactions catalyzed by dirhodium(II) tetraacetate, and that product is not necessarily the one predicted by presumed electronic preferences.