Diethyl 2-bromo-2-propargylmalonate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Diethyl 2-bromo-2-propargylmalonate
• 英文别名: Diethyl 2-bromo-2-prop-2-ynylpropanedioate
• 化学式: C₁₀H₁₃BrO₄
• 分子量: 277.115
• InChiKey: QZZDZGFUZCHYCU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  邻乙炔基联苯 、 Diethyl 2-bromo-2-propargylmalonate 在 2,2'-联吡啶 、 tetrakis(actonitrile)copper(I) hexafluorophosphate 、 sodium carbonate 作用下， 以 甲苯 为溶剂， 反应 12.0h， 以45%的产率得到
  参考文献：
  名称：

  铜催化的小α-溴羰基与联芳基或（Z）-芳基乙烯基乙炔之间的级联环化反应可直接合成二苯并环庚烷和相关化合物

  摘要：

  提出了铜催化的γ，小δ-不饱和的α-溴代羰基与联芳基或（Z）-芳基乙烯基乙炔的级联环化反应，以中等至高收率快速获得二苯并环庚烷和相关化合物。它提供了一个...

  DOI：

  10.1039/c6cc07727g
• 作为产物：
  描述：

  2-(2-丙炔-1-基)丙二酸二乙酯 在 sodium hydride 、 copper(ll) bromide 作用下， 以 二甲基亚砜 为溶剂， 以76%的产率得到Diethyl 2-bromo-2-propargylmalonate
  参考文献：
  名称：

  Mild halogenation of stabilized ester enolates by cupric halides

  摘要：

  The reactions of various stabilized ester enolates of 2-keto, 2-(alkoxycarbonyl), 2-phosphoryl, and 2-(benzenesulfonyl) esters with cupric chloride or cupric bromide have been examined. The reactions lead to 2-halo esters in good to excellent yields under mild condition. Enolates which contain an unsaturated functionality such as a double bond, a triple bond, or an allylic or a benzylic moiety react with high chemoselectivity.

  DOI：

  10.1021/jo00069a020

文献信息

• Copper-Catalyzed Cascade Radical Addition–Cyclization Halogen Atom Transfer between Alkynes and Unsaturated α-Halogenocarbonyls
  作者：Yuzhen Gao、Pengbo Zhang、Zhe Ji、Guo Tang、Yufen Zhao

  DOI：10.1021/acscatal.6b03033

  日期：2017.1.6

  addition/cyclization/halogen atom transfer between alkynes and α-halogeno-γ, δ-unsaturated carbonyl compounds for the synthesis of various substituted cyclopentenes is described. Since up to four Csp3–Csp2 bonds, two Csp3–Br bonds, and two carbocycles can be established in a single reaction, this 100% atom-efficient reaction exhibits the advantages of wide substrate scope, high functional group tolerance, and step-economics

  描述了Cu催化的炔烃与α-卤代-γ，δ-不饱和羰基化合物之间的级联自由基加成/环化/卤素原子转移，用于合成各种取代的环戊烯。由于在一个反应​​中最多可以建立四个Csp 3 -Csp 2键，两个Csp 3 -Br键和两个碳环，所以这种100％原子效率的反应具有底物范围宽，官能团耐受性高和一步经济学，它为取代环戊烯的合成提供了原子转移自由基加成/环化（串联ATRA-ATRC）过程的入口。
• Shi Xiao-Xin, Dai Li-Xin, J. Org. Chem., 58 (1993) N 17, S 4596-4598
  作者：Shi Xiao-Xin, Dai Li-Xin

  DOI：——

  日期：——
• Copper-catalyzed cascade annulation between α-bromocarbonyls and biaryl or (Z)-arylvinylacetylenes enabling a direct synthesis of dibenzocycloheptanes and related compounds
  作者：Danyang Lu、Yimei Wan、Lichun Kong、Gangguo Zhu

  DOI：10.1039/c6cc07727g

  日期：——

  A copper-catalyzed cascade annulation of [gamma],[small delta]-unsaturated [small alpha]-bromocarbonyls with biaryl or (Z)-arylvinylacetylenes is presented, giving an expeditious access to dibenzocycloheptanes and related compounds in moderate to high yields. It provides a...

  提出了铜催化的γ，小δ-不饱和的α-溴代羰基与联芳基或（Z）-芳基乙烯基乙炔的级联环化反应，以中等至高收率快速获得二苯并环庚烷和相关化合物。它提供了一个...
• Mild halogenation of stabilized ester enolates by cupric halides
  作者：Xiaoxin Shi、Lixin Dai

  DOI：10.1021/jo00069a020

  日期：1993.8

  The reactions of various stabilized ester enolates of 2-keto, 2-(alkoxycarbonyl), 2-phosphoryl, and 2-(benzenesulfonyl) esters with cupric chloride or cupric bromide have been examined. The reactions lead to 2-halo esters in good to excellent yields under mild condition. Enolates which contain an unsaturated functionality such as a double bond, a triple bond, or an allylic or a benzylic moiety react with high chemoselectivity.