bis(2,2,2-trifluoroethyl) 2-diazomalonate | 1446102-96-0

• 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: bis(2,2,2-trifluoroethyl) 2-diazomalonate
• 英文别名: 2-Diazomalonic acid bis(2,2,2-trifluoroethyl) ester；bis(2,2,2-trifluoroethyl) 2-diazopropanedioate
• CAS: 1446102-96-0
• 化学式: C₇H₄F₆N₂O₄
• 分子量: 294.11
• InChiKey: HSUHWKDXAAFOMI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  54.6
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  bis(2,2,2-trifluoroethyl) 2-diazomalonate 在 bis{rhodium[3,3'-(1,3-phenylene)bis(2,2-dimethylpropanoic acid)]} 、 scandium tris(trifluoromethanesulfonate) 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 bis(2,2,2-trifluoroethyl) 2-(2-(1,3-dioxoisoindolin-2-yl)-2-(6-(methoxycarbonyl)-1-methyl-1H-indol-3-yl)ethyl)malonate
  参考文献：
  名称：

  Catalytic Friedel–Crafts Reaction of Aminocyclopropanes

  摘要：

  A Lewis acid catalyzed Friedel-Crafts reaction between donor-acceptor aminocyclopropanes and indoles and other electron-rich aromatic compounds is reported. Indole alkylation at the C3 position was generally obtained for a broad range of functional groups and substitution patterns. In the case of C3-substituted indoles, C2 alkylation was observed. The reaction gives a rapid access to gamma amino acid derivatives present in numerous bioactive molecules.

  DOI：

  10.1021/ol401616a
• 作为产物：
  描述：

  bis(2,2,2-trifluoroethyl) malonate 在 对甲苯磺酰叠氮 、 caesium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 bis(2,2,2-trifluoroethyl) 2-diazomalonate
  参考文献：
  名称：

  铜催化的区域选择性级联烷基化和重氮酯喹啉N氧化物的环缩合：直接进入共轭π系统

  摘要：

  已经成功实现了廉价的铜催化级联区域选择性烷基化，然后将喹啉N-氧化物与α-重氮酯进行环缩合，从而提供了含杂芳烃的共轭π系统。所开发的方法简单，直接且经济，具有广泛的基板范围。探索了铜催化剂在CH键功能化和路易斯酸促进的环化中的双重作用。

  DOI：

  10.1002/chem.201602493

文献信息

• Rh(III)-Catalyzed Regio- and Chemoselective [4 + 1]-Annulation of Azoxy Compounds with Diazoesters for the Synthesis of 2<i>H</i>-Indazoles: Roles of the Azoxy Oxygen Atom
  作者：Zhen Long、Zhigang Wang、Danni Zhou、Danyang Wan、Jingsong You

  DOI：10.1021/acs.orglett.7b00631

  日期：2017.6.2

  tandem C–H alkylation/intramolecular decarboxylative cyclization of azoxy compounds with diazoesters for the synthesis of 3-acyl-2H-indazoles is disclosed. The azoxy instead of the azo group enables a distinct approach for cyclative capture, leading to a [4 + 1]-annulation rather than a classic [4 + 2] manner. The azoxy oxygen atom is traceless after annulation, and further removal from the product is

  揭示了用Rh（III）催化的重氮化合物与重氮酸酯的串联C–H烷基化/分子内脱羧环化反应，可合成3-酰基-2 H-吲唑。取代偶氮基团的是偶氮氧基团，从而实现了一种独特的环化捕获方法，从而导致了[4 +1]环化，而不是经典的[4 + 2]方式。环氧化后，z氧基氧原子是无痕的，不需要进一步从产物中除去。该反应具有对不对称的乙氧基苯的完全区域选择性和单芳基二烯氧化物的相容性。
• Iridium-Catalysed Cascade Synthesis of Oxindoles Using Diazo Compounds: A Quick Entry to C-7-Functionalized Oxindoles
  作者：Ujjwal Karmakar、Debapratim Das、Rajarshi Samanta

  DOI：10.1002/ejoc.201700214

  日期：2017.5.18

  A cascade iridium-catalysed oxindole synthesis was achieved using pyridyl-protected anilines and bis(2,2,2-trifluoroethyl) 2-diazomalonate. The developed protocol is simple and scalable, and has a broad scope and excellent regioselectivity. The pyridyl directing group can easily be removed. The method was further extended to give C-7-functionalized oxindole derivatives in a straightforward manner.

  使用吡啶基保护的苯胺和双 (2,2,2-三氟乙基) 2-重氮丙二酸酯实现了级联铱催化的羟吲哚合成。开发的协议简单且可扩展，具有广泛的范围和出色的区域选择性。吡啶基导向基团可以很容易地去除。该方法进一步扩展到以直接的方式得到 C-7 官能化的羟吲哚衍生物。已经探索了双 (2,2,2-三氟乙基) 2-重氮丙二酸酯在羟吲哚制备中的作用。
• Rhodium(III)-Catalyzed Regioselective Direct C4-Alkylation and C2-Annulation of Indoles: Straightforward Access to Indolopyridone
  作者：Aniruddha Biswas、Rajarshi Samanta

  DOI：10.1002/ejoc.201701755

  日期：2018.3.29

  C4‐alkylation and C2‐annulation of indole derivative has been developed by using variable diazo esters. Fine tuning of the reactivity of diazo esters leads to control in regioselectivity with wide scope and functional‐group tolerance. A straightforward approach has been established to furnish an indolopyridone scaffold.

  通过使用可变的重氮酯开发了Rh III催化的吲哚衍生物的位点C4烷基化和C2环化。对重氮酯反应性的微调可以控制区域选择性，具有宽范围和官能团耐受性。已经建立了一种简单的方法来提供吲哚并吡啶酮支架。
• Enantioselective Synthesis of Chiral Cyclopent-2-enones by Nickel-Catalyzed Desymmetrization of Malonate Esters
  作者：Somnath Narayan Karad、Heena Panchal、Christopher Clarke、William Lewis、Hon Wai Lam

  DOI：10.1002/anie.201805578

  日期：2018.7.16

  enantioselective synthesis of highly functionalized chiral cyclopent-2-enones by the reaction of alkynyl malonate esters with arylboronic acids is described. These desymmetrizing arylative cyclizations are catalyzed by a chiral phosphinooxazoline/nickel complex, and cyclization is enabled by the reversible E/Z isomerization of alkenylnickel species. The general methodology is also applicable to the synthesis of

  描述了通过丙二酸炔基酯与芳基硼酸的反应的高官能化手性环戊-2-烯酮的对映选择性合成。通过手性膦基恶唑啉/镍络合物催化这些脱对称芳基环化反应，并且通过烯基镍物质的可逆E / Z异构化作用实现环化反应。通用方法也适用于1,6-二氢吡啶3-3（2H）-one的合成。
• Cobalt(III)-Catalyzed Directed CH Coupling with Diazo Compounds: Straightforward Access towards Extended π-Systems
  作者：Dongbing Zhao、Ju Hyun Kim、Linda Stegemann、Cristian A. Strassert、Frank Glorius

  DOI：10.1002/anie.201411994

  日期：2015.4.7

  The first highly efficient and scalable cobalt‐catalyzed directed CH functionalization with carbene precursors is presented. This methodology provides a modular route towards a new class of conjugated polycyclic hydrocarbons with tunable emission wavelengths both in solution and in the solid state.

  介绍了卡宾前体的第一个高效且可扩展的钴催化的定向CH功能化。该方法学提供了通往一类新型的共轭多环烃的模块化途径，该共轭多环烃在溶液和固态下均具有可调的发射波长。