2-but-2-ynyl-2,3-bis-ethoxycarbonyl-3-prop-2-ynyl-succinic acid diethyl ester | 1300749-67-0

• 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: 2-but-2-ynyl-2,3-bis-ethoxycarbonyl-3-prop-2-ynyl-succinic acid diethyl ester
• 英文别名: tetraethyl nona-1,7-diyne-4,4,5,5-tetracarboxylate；tetraethyl 1,7-nonadiyne-4,4,5,5-tetracarboxylate；Tetraethyl nona-1,7-diyne-3,3,4,4-tetracarboxylate
• CAS: 1300749-67-0
• 化学式: C₂₁H₂₈O₈
• 分子量: 408.449
• InChiKey: WAUFEWQLSRPTFD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  29
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-but-2-ynyl-2,3-bis-ethoxycarbonyl-3-prop-2-ynyl-succinic acid diethyl ester 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 37.5h， 生成 (-)-6,6,7,7-tetraethyl 3-methyl 4-(2-chlorophenyl)-1-methyl-5,8-dihydroisoquinoline-3,6,6,7,7-pentacarboxylate
  参考文献：
  名称：

  铑催化的Atroposelective [2 + 2 + 2]环加成邻用腈取代的苯基二炔：的影响邻对区域选择性和对映体选择性的取代基

  摘要：

  阳离子铑（I）/（S）-H 8 -BINAP络合物催化的对位选择性[2 + 2 + 2]环加成（o -卤代苯基）二炔与腈。有趣的是，区域和对映体选择性高度取决于二炔的苯基上的邻位取代基。当邻位取代基为甲氧基和甲氧基羰基时，轴向手性3-芳基吡啶是主要产物，而对映选择性显着降低。另一方面，当邻 取代基是烷基，切换区域选择性以高收率得到非手性6-芳基吡啶。

  DOI：

  10.1021/acs.orglett.6b00791
• 作为产物：
  描述：

  2,3,3-tris-ethoxycarbonyl-hept-5-ynoic acid ethyl ester 、 3-溴丙炔 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 40.5h， 以86%的产率得到2-but-2-ynyl-2,3-bis-ethoxycarbonyl-3-prop-2-ynyl-succinic acid diethyl ester
  参考文献：
  名称：

  Rhodium-Catalyzed Decarboxylative Cycloaddition Route to Substituted Anilines

  摘要：

  A convenient method for preparing substituted anilines via a Rh-catalyzed [2 + 2 + 2] cycloaddition reaction of diynes and 2-oxazolone was discovered. The initial cycloaddition adducts undergo facile decarboxylation of carbon dioxide to afford aniline products. Reaction conditions are mild, and only 3 mol % Rh catalyst is required. High regioselectivity was observed when an unsymmetrical diyne was used as a starting material.

  DOI：

  10.1021/jo200236h

文献信息

• Highly Stereo- and Regioselective Hydrocarboxylation of Diynes with Carbon Dioxide
  作者：Tao Cao、Shengming Ma

  DOI：10.1021/acs.orglett.6b00028

  日期：2016.4.1

  A nickel-catalyzed three-component hydrocarboxylation of diynes with ZnEt2 and CO2 (1 atm) is disclosed. With this method, symmetric/nonsymmetric diynes could be reacted smoothly with very high stereo- and regioselectivity, affording conjugated 2,4-alkadienoic acids incorporated with five- or six-membered rings efficiently. A stepwise non-oxidative cyclometalation mechanism was proposed based on careful

  公开了用ZnEt 2和CO 2（1atm）的二炔的镍催化的三组分加氢羧化。用这种方法，对称/不对称二炔可以以非常高的立体选择性和区域选择性平滑反应，从而有效地提供了结合有五元或六元环的共轭2,4-链二烯酸。在仔细的机理研究的基础上，提出了一种逐步的非氧化性环金属化机理。
• Rhodium-Catalyzed Atroposelective [2 + 2 + 2] Cycloaddition of <i>Ortho</i>-Substituted Phenyl Diynes with Nitriles: Effect of <i>Ortho</i> Substituents on Regio- and Enantioselectivity
  作者：Kenichi Kashima、Kota Teraoka、Hidehiro Uekusa、Yu Shibata、Ken Tanaka

  DOI：10.1021/acs.orglett.6b00791

  日期：2016.5.6

  Axially chiral 3-(2-halophenyl)pyridines were successfully synthesized in high yields with excellent enantioselectivity by the cationic rhodium(I)/(S)-H8–BINAP complex-catalyzed atroposelective [2 + 2 + 2] cycloaddition of (o-halophenyl)diynes with nitriles. Interestingly, regio- and enantioselectivity highly depend on ortho substituents on the phenyl group of diynes. When the ortho substituents were

  阳离子铑（I）/（S）-H 8 -BINAP络合物催化的对位选择性[2 + 2 + 2]环加成（o -卤代苯基）二炔与腈。有趣的是，区域和对映体选择性高度取决于二炔的苯基上的邻位取代基。当邻位取代基为甲氧基和甲氧基羰基时，轴向手性3-芳基吡啶是主要产物，而对映选择性显着降低。另一方面，当邻 取代基是烷基，切换区域选择性以高收率得到非手性6-芳基吡啶。
• Rhodium-Catalyzed Decarboxylative Cycloaddition Route to Substituted Anilines
  作者：Kainan Zhang、Janis Louie

  DOI：10.1021/jo200236h

  日期：2011.6.3

  A convenient method for preparing substituted anilines via a Rh-catalyzed [2 + 2 + 2] cycloaddition reaction of diynes and 2-oxazolone was discovered. The initial cycloaddition adducts undergo facile decarboxylation of carbon dioxide to afford aniline products. Reaction conditions are mild, and only 3 mol % Rh catalyst is required. High regioselectivity was observed when an unsymmetrical diyne was used as a starting material.