1-methylenedispiro<2.0.2.1>heptane | 50874-26-5

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1-methylenedispiro<2.0.2.1>heptane
• 英文别名: (3RS)-1-methylenedispiro[2.0.2.1]heptane；methylene-<3>-triangulane；1-Methylidenedispiro[2.0.2~4~.1~3~]heptane；5-methylidenedispiro[2.0.24.13]heptane
• CAS: 50874-26-5
• 化学式: C₈H₁₀
• 分子量: 106.167
• InChiKey: SKAJZUHJLQIZBE-UHFFFAOYSA-N

物化性质

• 沸点：
  145.1±7.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-methylenedispiro<2.0.2.1>heptane 在 [Rh(C₇H₁₅COO)2]2 氢氧化钾 、 lithium aluminium tetrahydride 作用下， 以 乙醚 、 乙醇 、 二氯甲烷 为溶剂， 反应 8.5h， 生成 (1RS,3SR,4SR)-(trispiro[2.0.0.2.1.1]non-1-yl)methanol
  参考文献：
  名称：

  The First Enantiomerically Pure [n]Triangulanes and Analogues: σ-[n]Helicenes with Remarkable Features

  摘要：

  (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.

  DOI：

  10.1002/1521-3765(20020215)8:4<828::aid-chem828>3.0.co;2-y
• 作为产物：
  描述：

  1-methylenespiro[2.2]pentane 在 正丁基锂 、 potassium tert-butylate 作用下， 以 乙醚 、 二甲基亚砜 、 正戊烷 为溶剂， 反应 1.0h， 生成 1-methylenedispiro<2.0.2.1>heptane
  参考文献：
  名称：

  Zefirov, N. S.; Lukin, K. A.; Kozhushkov, S. I., Journal of Organic Chemistry USSR (English Translation), 1989, vol. 25, # 2.1, p. 278 - 284

  摘要：

  DOI：

文献信息

• Triangulanes: stereoisomerism and general method of synthesis
  作者：N. S. Zefirov、S. I. Kozhushkov、T. S. Kuznetsova、O. V. Kokoreva、K. A. Lukin、B. I. Ugrak、S. S. Tratch

  DOI：10.1021/ja00177a034

  日期：1990.10

  The class of spirocondensed cyclopropanes, triangulanes, is defined and stereochemical problems of unbranched triangulanes (UTs) are considered from an algebraic-combinatorial point of view. The general method of triangulane synthesis that consists of the addition of chloromethylcarbene to methylenecyclopropanes with subsequent dehydrochlorination and final cyclopropanation of the resulting methylenetriangulanes

  定义了螺环缩合环丙烷类三角烷，并从代数组合的角度考虑了无支链三角烷 (UT) 的立体化学问题。Triangulane 合成的一般方法包括将氯甲基卡宾加成到亚甲基环丙烷中，随后脱氯化氢和最终得到的亚甲基三环丙烷环丙烷化，建议并实现了该家族的 [5]-和 [6]-成员
• ZEFIROV, N. S.;LUKIN, K. A.;KOZHUSHKOV, S. I.;KUZNETSOVA, T. S.;DOMAREV, +, ZH. ORGAN. XIMII, 25,(1989) N, S. 312-319
  作者：ZEFIROV, N. S.、LUKIN, K. A.、KOZHUSHKOV, S. I.、KUZNETSOVA, T. S.、DOMAREV, +

  DOI：——

  日期：——
• ZEFIROV, NIKOLAI S.;KOZHUSHKOV, SERGE I.;KUZNETSOVA, T. S.;KOKOREVA, O. V+, J. AMER. CHEM. SOC., 112,(1990) N1, C. 7702-7707
  作者：ZEFIROV, NIKOLAI S.、KOZHUSHKOV, SERGE I.、KUZNETSOVA, T. S.、KOKOREVA, O. V+

  DOI：——

  日期：——
• Zefirov, N. S.; Lukin, K. A.; Kozhushkov, S. I., Journal of Organic Chemistry USSR (English Translation), 1989, vol. 25, # 2.1, p. 278 - 284
  作者：Zefirov, N. S.、Lukin, K. A.、Kozhushkov, S. I.、Kuznetsova, T. S.、Domarev, A. M.、Sosonkin, I. M.

  DOI：——

  日期：——
• 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.