bicyclopropylidenecarboxylic acid | 151964-06-6

• 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: bicyclopropylidenecarboxylic acid
• 英文别名: 2-Cyclopropylidenecyclopropane-1-carboxylic acid
• CAS: 151964-06-6
• 化学式: C₇H₈O₂
• mdl: MFCD19228886
• 分子量: 124.139
• InChiKey: RKLKOHMFBLGRGH-UHFFFAOYSA-N

物化性质

• 沸点：
  256.5±9.0℃ (760 Torr)
• 密度：
  1.520±0.06 g/cm3 (20 ºC 760 Torr)
• 闪点：
  114.0±13.4℃

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.571
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bicyclopropylidenecarboxylic acid 在 lithium 作用下， 以 四氢呋喃 、 氨 为溶剂， 反应 2.0h， 以76%的产率得到trans-2-Carboxy-bicyclopropyl
  参考文献：
  名称：

  Loehr, Sandra; Jacobi, Carsten; Johann, Andre, European Journal of Organic Chemistry, 2000, # 17, p. 2979 - 2990

  摘要：

  DOI：
• 作为产物：
  描述：

  1-溴-1-环丙基环丙烷 在 正丁基锂 、 potassium tert-butylate 作用下， 生成 bicyclopropylidenecarboxylic acid
  参考文献：
  名称：

  铁催化的三环活化的双环亚丙基活化三唑

  摘要：

  在无外部氧化剂的条件下，用铁催化剂完成了氧甲基化的双环亚丙基的C–H / C–C官能化。双环亚丙基与独特的铁（II）催化剂的独特反应性相结合，可实现化学选择性的C–C裂解，从而可合成异喹诺酮，游离异喹诺酮或双螺并稠合的异喹诺酮。机理研究为通过消除β -C进行C–C裂解提供了有力的支持。还观察到了罕见的三氟甲基芳烃的单选择性C–F / C–H键官能化。

  DOI：

  10.1021/acscatal.0c04748

文献信息

• Domino Heck–Diels–Alder Reactions of Monosubstituted Bicyclopropylidenes
  作者：Baris Yucel、Mathias Noltemeyer、Armin de Meijere

  DOI：10.1002/ejoc.200700999

  日期：2008.2

  complex 23b undergoing deboropalladation rather than dehydropalladation. Similarly, reactions of tributylstannyl- and hydroxydimethylsilyl-substituted bicyclopropylidenes 8c–d with 9 and tert-butyl acrylate gave the tert-butyl phenylspirooctenecarboxylate 26 via the diene 24 formed by demetallopalladation processes. The reaction of methyl 1,1′-bicyclopropylidene-2-carboxylate (8e) with iodobenzene (9) in

  涉及频哪醇双环亚丙基硼酸酯 (8b)、碘苯 (9) 和丙烯酸甲酯 (12) 在 Jeffery 条件下的三组分多米诺 Heck-Diels-Alder 反应 [Pd(OAc)2、PPh3、K2CO3、Et4NCl、MeCN] 产生了混合物苯基螺[2.5]辛烯硼酸酯syn/anti-(E)-14b和苯基螺辛烯羧酸甲酯25的产率分别为25%和38%。主要产物25很可能是通过高烯丙基钯络合物23b进行脱硼钯化而不是脱氢钯化而形成的。类似地，三丁基甲锡烷基和羟基二甲基甲硅烷基取代的双环亚丙基 8c-d 与 9 和丙烯酸叔丁酯通过脱金属钯化过程形成的二烯 24 得到叔丁基苯基螺辛烯羧酸酯 26。甲基1的反应，在丙烯酸​​叔丁酯 (13) 的存在下，1'-双环亚丙基-2-羧酸酯 (8e) 与碘苯 (9) 提供了区域异构和非对映异构螺辛烯顺/反-(E)-15e 和顺/反-( Z)-15e 的产率分别为 69%
• The First Enantiomerically Pure [n]Triangulanes and Analogues: σ-[n]Helicenes with Remarkable Features
  作者：Armin de Meijere、Alexander F. Khlebnikov、Sergei I. Kozhushkov、Rafael R. Kostikov、Peter R. Schreiner、Alexander Wittkopp、Christopher Rinderspacher、Henning Menzel、Dmitrii S. Yufit、Judith A. K. Howard

  DOI：10.1002/1521-3765(20020215)8:4<828::aid-chem828>3.0.co;2-y

  日期：2002.2.15

  (M)-(-)- and (P)-(+)-Thspiro-[2.0.0.2.1.1]nonanes [(M)- and (P)-3] as well as (M)-(-)- and (P)-(+)-tetraspiro[2.0.0.0.2.1.1.1]undecanes [(M)- and (P)4]-enantiomerically pure unbranched [4]- and [5]triangulanes-have been prepared starting from racemic bicyclopropylidenecarboxylic [(1RS)-12] and exo-dispiro[2.0.2.1]heptane-1-carboxylic [(lRS,3SR)-13] acids. The optical resolutions of rac-12 and rac-13 furnished enantiomerically pure acids (S)-(+)12, (R)-(-)-12, (1R,3S)-(-)-13, and (1S,3R)-(+)-13. The ethyl ester (R)-25 of the acid (R)-(-)-12 was cyclopropanated to give carboxylates (1R,3R)-26 and (1R,3S)-26. The ester (IR,3S)-26 and acids (1R,3S)-13 and (IS,3R)-13 were converted into enantiomerically pure methylene[3]triangulanes (S)-(-)and (R)-(+)-28. An alternative approach consisted of an enzymatic deracemization of endo-[(1SR,3SR)-dispiro[2.0.2. 1]heptyl] methanol (rac-20) or anti- [(1SR.3RS)-4-methylenespiropentyl]methanol (rac-18). This afforded (S)-(-)- and (R)-(+)-28 (starting from rac-20), as well as enantiomerically pure (M)-(-)- and (P)-(+)-l,4-dimethylenespiropentanes [(M)- and (P)-23] starting from rac-18. The methylenetriangulanes (S)-(-)- and (R)-(+)-28 were cyclopropanated furnishing (M)- and (P)-3. The rhodium-catalyzed cycloaddition of ethyl diazoacetate onto (S)-(-)- and (R)(+)-28 yielded four diastereomeric ethyl trispiro[2.0.0.2.1.1]nonane-1-carboxylates in approximately equal proportions. The enantiomerically pure esters (1R,3S,4S)- and (1S,3R,4R)-30 were isolated by careful distillation and then transformed into [5]triangulanes (M)and (P)-4 using the same sequence of reactions Lis applied for (M)- and (P)-3. The structures of the key intermediates (R)-12 and rac-31 were confirmed by X-ray analyses. Although [4]- and [5]triangulanes have no chromophore which would lead to any significant absorption above 200 nm. they have remarkably high specific rotations even at 589 nm with [alpha](20)(1)) = -192.7 [(M)-3, c=1.18, CHCl3)] or + 373.0 [(P)-4, c=1.18, CHCl3]. This remarkable optical rotatation is in line with their helical arrangement of sigma bonds, as confirmed by a full valence space single excitation configuration interaction treatment (SCI) in conjunction with DFT computations at the B3LYP/TZVP//B3LYP/6-31 +G(d,p) level of theory which reproduce the ORD very well. Thus, it is appropriate to call the helically shaped unbranched [n]triangulanes the "sigma-[n]helicenes", representing the sigma-bond analogues of the aromatic [n]helicenes.
• De Meijere; Kozhushkov; Zefirov, Synthesis, 1993, # 7, p. 681 - 683
  作者：De Meijere、Kozhushkov、Zefirov

  DOI：——

  日期：——
• Loehr, Sandra; Jacobi, Carsten; Johann, Andre, European Journal of Organic Chemistry, 2000, # 17, p. 2979 - 2990
  作者：Loehr, Sandra、Jacobi, Carsten、Johann, Andre、Gottschalk, Gerhard、Meijere, Armin de

  DOI：——

  日期：——
• Iron-Catalyzed Triazole-Enabled C–H Activation with Bicyclopropylidenes
  作者：Jiayu Mo、Antonis M. Messinis、João C. A. Oliveira、Serhiy Demeshko、Franc Meyer、Lutz Ackermann

  DOI：10.1021/acscatal.0c04748

  日期：2021.2.5

  C–H/C–C functionalizations with oxymethylated bicyclopropylidenes were accomplished with an iron catalyst under external oxidant-free conditions. The combination of the unique reactivity of bicyclopropylidenes with a robust iron(II) catalyst enabled C–C cleavages in a chemoselective fashion, which allows for the synthesis of isoquinolones, free isoquinolones, or bispiro-fused isoquinolones. Mechanistic

  在无外部氧化剂的条件下，用铁催化剂完成了氧甲基化的双环亚丙基的C–H / C–C官能化。双环亚丙基与独特的铁（II）催化剂的独特反应性相结合，可实现化学选择性的C–C裂解，从而可合成异喹诺酮，游离异喹诺酮或双螺并稠合的异喹诺酮。机理研究为通过消除β -C进行C–C裂解提供了有力的支持。还观察到了罕见的三氟甲基芳烃的单选择性C–F / C–H键官能化。