t-Butyl oximinoacetoacetate | 101798-63-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: t-Butyl oximinoacetoacetate
• CAS: 101798-63-4
• 化学式: C₈H₁₅NO₃
• 分子量: 173.212
• InChiKey: OMLFWQYAEFCJMX-UHFFFAOYSA-N

物化性质

• 沸点：
  260.6±23.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.57
• 重原子数：
  12.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  58.89
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  t-Butyl oximinoacetoacetate 在 sodium acetate 、 乙酸酐 、 溶剂黄146 、 锌 作用下， 反应 4.0h， 生成 tert-Butyl 5-acetoxymethyl-4-butyl-3-methyl-1H-pyrrole-2-carboxylate
  参考文献：
  名称：

  Porphyrins with exocyclic rings. Part 19: Efficient syntheses of phenanthrolinoporphyrins

  摘要：

  5-Nitro-1,10-phenanthrolines react with isocyanoacetate esters in the presence of DBU in THF to give excellent yields of the corresponding phenanthrolinopyrroles. These were condensed with acetoxymethylpyrroles using catalytic quantities Of p-tolenesulfonic acid in acetic acid to give dipyrrylmethanes, but these structures proved to be poorly suited for porphyrin synthesis due to the electron-withdrawing nature of the fused phenanthroline unit. However, phenanthrolinopyrrole ethyl esters could be converted to the corresponding alpha-unsubstituted pyrroles with KOH in ethylene glycol at 180-190 degrees C and these condensed with 2 equiv of acetoxymethylpyrroles in refluxing acetic acid-isopropyl alcohol to give tripyrranes. In a one pot procedure, tripyrrane di-tert-butyl esters were treated with TFA at room temperature to cleave the protective groups, diluted with dichloromethane, reacted with pyrrole dialdehydes and oxidized to afford phenanthrolinoporphyrins in 52-83% yield. These conditions also allow the synthesis of porphyrins with additional fused acenaphthylene or phenanthrene rings. Although the UV-vis spectra for these porphyrins are unexceptional, the presence of an external coordination site allows many potential applications to be considered. Porphyrins with two phenanthroline units could not be prepared by the '3 + 11 strategy. Instead, alpha-unsubstituted phenanthrolinopyrroles were reacted with a bis(dimethylaminomethyl)pyrrole in refluxing acetic acid to give moderate yields of the corresponding opp-diphenanthrolinoporphyrins. In one case, a triphenanthrolitioporphyrin and trace amounts of an adj-diphenanthrolinoporphyrin were formed as by-products. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.09.089
• 作为产物：
  描述：

  乙酰乙酸叔丁酯 在 盐酸羟胺 、 sodium acetate 作用下， 生成 t-Butyl oximinoacetoacetate
  参考文献：
  名称：

  连续铑催化的正式[3 + 3]环加成反应和重氮吲哚并咪唑与偶氮化合物的芳香化反应区域合成吲哚并吡嗪

  摘要：

  通过连续的Rh催化的正式[3 + 3]环加成反应以及各种重氮吲哚并咪唑与叠氮基的芳构化反应，证明了制备吲哚并吡嗪的区域选择性合成方法。因为先前报道的合成方法提供了吲哚并吡嗪的混合物，所以从区域选择性的角度来看，使用不对称叠氮基的本方法具有很强的优势。

  DOI：

  10.1021/acs.joc.8b00115

文献信息

• Rh^II-Catalyzed [3+2] Cycloaddition of 2 <i>H</i>-Azirines with<i>N</i>-Sulfonyl-1,2,3-Triazoles
  作者：Yun-Zhou Zhao、Hai-Bin Yang、Xiang-Ying Tang、Min Shi

  DOI：10.1002/chem.201406460

  日期：2015.2.23

  RhII‐catalyzed intermolecular [3+2] cycloaddition of 2 H‐azirines with N‐sulfonyl‐1,2,3‐triazoles is disclosed, in which a series of fully functionalized pyrroles is produced via rhodium azavinyl carbene intermediates. A distinct feature of this reaction is that the azavinyl carbene serves as a [2 C] equivalent, instead of as [1 C] or aza‐[3 C] synthons, which have been reported previously in cyclopropanations

  Rh II催化的2 H-叠氮基与N-磺酰基-1,2,3-三唑的分子间[3 + 2]环加成反应 ，其中通过氮杂乙烯基卡宾铑中间体生产了一系列功能完全的吡咯。该反应的显着特征是，氮杂乙烯基卡宾可作为[2 C]等效物，而不是先前在环丙烷和[3+ n ]环加成中报道的[1 C]或aza- [3 C]合成子。。此外，该方法学也已成功应用于URB447的全合成以及阿托伐他汀（立普妥）的正式合成。
• Synthesis of Highly Substituted Azepanones from 2<i>H</i>-Azirines by a Stepwise Annulation/Ring-Opening Sequence
  作者：Alexandre Dupas、Pierre-Alexandre Lhotellier、Gérard Guillamot、Christophe Meyer、Janine Cossy

  DOI：10.1021/acs.orglett.9b00999

  日期：2019.5.17

  Bicyclic aziridines possessing a 1-azabicyclo[4.1.0]heptan-2-one core were prepared from 2H-azirines by a stepwise annulation sequence involving a diastereoselective allylindanation, an N-acylation, and a ring-closing metathesis to construct the six-membered ring. After hydrogenation or functionalization of the olefin, regioselective ring opening of the resulting azabicyclic compounds with carboxylic

  具有2个H-叠氮基的逐步环化序列由非对映选择性烯丙基化，N-酰化和一个闭环易位构筑，由两个H-叠氮基制备具有1-氮杂双环[4.1.0]庚-2-基的双环氮丙啶。环。烯烃氢化或官能化后，将所得氮杂双环化合物与羧酸（或硫亲核试剂）进行区域选择性开环，得到具有氮原子的α和β位置具有酯部分或三氟甲基基团和四取代碳原子的高度取代的氮杂酮。 ， 分别。
• Organocatalytic Asymmetric Neber Reaction for the Synthesis of 2<i>H</i>-Azirine Carboxylic Esters
  作者：Shota Sakamoto、Tsubasa Inokuma、Yoshiji Takemoto

  DOI：10.1021/ol2026747

  日期：2011.12.16

  The first enantioselective Neber reaction of β-ketoxime sulfonates catalyzed by a bifunctional thiourea has been developed. The reaction proceeds stereoselectively with 5 mol % of the catalyst to give the 2H-azirine carboxylic esters in good yields with up to 93% ee. In addition, the resulting azirines can be successfully employed in the stereoselective synthesis of di- and trisubstituted aziridines

  已经开发了由双官能硫脲催化的β-酮肟磺酸盐的第一个对映选择性Neber反应。用5mol％的催化剂使反应立体选择性地进行，从而以高达93％ee的高收率得到2 H-叠氮基羧酸酯。另外，所得的叠氮基可以成功地用于二和三取代的氮丙啶的立体选择性合成中。
• Boehme, Roswitha; Breitmaier, Eberhard, Synthesis, 1999, # 12, p. 2096 - 2102
  作者：Boehme, Roswitha、Breitmaier, Eberhard

  DOI：——

  日期：——
• Al-Qawasmeh, Raed A.; Al-Tel, Taleb H.; Abdel-Jalil, Raid J., Chemistry Letters, 1999, # 7, p. 541 - 542
  作者：Al-Qawasmeh, Raed A.、Al-Tel, Taleb H.、Abdel-Jalil, Raid J.、Voelter, Wolfgang

  DOI：——

  日期：——