2,3,4-trimethyl-3-pentyl diazoacetoacetate | 127236-65-1

• 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: 2,3,4-trimethyl-3-pentyl diazoacetoacetate
• 英文别名: (E)-3-diazonio-4-oxo-4-(2,3,4-trimethylpentan-3-yloxy)but-2-en-2-olate
• CAS: 127236-65-1
• 化学式: C₁₂H₂₀N₂O₃
• 分子量: 240.302
• InChiKey: SLYOIJPVWPYLRY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  6
• 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：

  2,3,4-trimethyl-3-pentyl diazoacetoacetate 生成 3-acetyl-5,5-diisopropyldihydro-2(3H)-furanone
  参考文献：
  名称：

  DOYLE, MICHAEL P.;BAGHERI, VAHID;PEARSON, MATTHEW M.;EDWARDS, JOHN D., TETRAHEDRON LETT., 30,(1989) N0, C. 7001-7004

  摘要：

  DOI：
• 作为产物：
  描述：

  2,3,4-三甲基-3-戊醇 在 对甲苯磺酰叠氮 、 三乙胺 作用下， 以 5,5-dimethyl-1,3-cyclohexadiene 、 乙腈 为溶剂， 反应 22.0h， 生成 2,3,4-trimethyl-3-pentyl diazoacetoacetate
  参考文献：
  名称：

  铜催化重氮化合物的对映选择性氧炔化

  摘要：

  允许将亲核试剂和亲电试剂添加到重氮化合物上的对映选择性催化方法可以快速进入重要的构建模块。在此，我们报告了使用乙炔基苯并氧醇-(on)e 试剂和简单的铜双恶唑啉催化剂对重氮化合物进行高度对映选择性的氧炔基化反应。获得的α-苯甲酰氧基炔丙酯是有用的结构单元，使用其他方法难以以对映体纯形式合成。所得产物可以有效地转化为邻二醇和α-羟基炔丙酯而不会损失对映体纯度。

  DOI：

  10.1021/jacs.7b04756

文献信息

• Ethynylbenziodazolones (EBZ) as Electrophilic Alkynylation Reagents for the Highly Enantioselective Copper‐Catalyzed Oxyalkynylation of Diazo Compounds
  作者：Durga Prasad Hari、Lionel Schouwey、Verity Barber、Rosario Scopelliti、Farzaneh Fadaei‐Tirani、Jerome Waser

  DOI：10.1002/chem.201900950

  日期：2019.7.17

  radicals and nucleophiles, yet they present limited possibilities for further structure and reactivity modification. Herein, the first synthesis is reported for the corresponding ethynylbenziodazolone (EBZ) reagents, in which the oxygen atom in the iodoheterocycle is replaced by a nitrogen atom. The substituent on the nitrogen enables further fine‐tuning of the reagent structure and reactivity. EBZ reagents

  乙炔基苯并恶唑（EBX）环状高价碘试剂现已确立为自由基和亲核试剂烷基化的试剂，但它们为进一步的结构和反应性修饰提供了有限的可能性。在此，报道了相应乙炔基苯并偶氮酮（EBZ）试剂的第一次合成，其中碘杂环中的氧原子被氮原子取代。氮上的取代基可进一步微调试剂的结构和反应性。EBZ试剂可通过一步步骤轻松地从相应的苯甲酰胺中获得，并具有与EBX试剂相当的反应性。特别是，它们被用于重氮化合物的不对称铜催化的氧炔基化反应中，
• Highly selective γ-lactone syntheses by intramolecular carbenoid carbon-hydrogen insertion in rhodium(II) carboxylate and rhodium(II) carboxamide catalyzed reactions of diazo esters
  作者：Michael P. Doyle、Vahid Bagheri、Matthew M. Pearson、John D. Edwards

  DOI：10.1016/s0040-4039(01)93408-2

  日期：——

  Rhodium(II) acetate and rhodium(II) acetamide catalyzed decomposition of diazo esters forms γ-lactones in high yield and with exceptionally high regio- and diastereoselectivity.

  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。
• 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.
• Electronic Effects in Dirhodium(II) Carboxylates. Linear Free Energy Relationships in Catalyzed Decompositions of Diazo Compounds and CO and Isonitrile Complexation
  作者：Michael C. Pirrung、Andrew T. Morehead

  DOI：10.1021/ja00099a017

  日期：1994.10

  A linear free energy analysis of substituent effects in rhodium carboxylate complexes has been conducted. Two reactions of diazo compounds involving intramolecular competition between (1) O-ylide formation and secondary C-H insertion, and (2) tertiary C-H and primary C-H insertion were studied as well as complexation effects on the IR frequencies of CO and tert-butyl isocyanide. Aliphatic and aromatic carboxylate complexes were included. Regression equations that describe these processes include contributions from sigma(alpha) (polarizability) and sigma(F) (field effects) and, for the benzoates, sigma(R) (resonance). Complexes that deviate from the LFER include rhodium trifluoroacetate and rhodium triptycenecarboxylate, and their behavior was explained through (partial) release of the free carbene. The effect of ligand polarizability on selectivity in these reactions was interpreted as evidence for the importance of backbonding from rhodium to the carbene carbon in the product-determining step. The ability of these complexes to backbond was shown through the complexation study. Higher selectivity with increasing ability to backbond is analogous to other carbenes such as difluorocarbene. Increased selectivity engendered by backbonding could occur by facilitating the reversal of an intermediate complex between the carbenoid and the C-H bond undergoing insertion. Increased selectivity engendered by field effects and polarizability could be explained by increased selectivity for electron-rich sites.