(1S,3R)-(+)-dispiro[2.0.2.1]heptane-1-carboxylic acid | 427893-02-5

• 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: (1S,3R)-(+)-dispiro[2.0.2.1]heptane-1-carboxylic acid
• 英文别名: (4R,5S)-dispiro[2.0.24.13]heptane-5-carboxylic acid
• CAS: 427893-02-5
• 化学式: C₈H₁₀O₂
• 分子量: 138.166
• InChiKey: FSZRAZFFCSDOJC-SVGQVSJJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  (1S,3R)-(+)-dispiro[2.0.2.1]heptane-1-carboxylic acid 在 吡啶 、 lithium aluminium tetrahydride 、 potassium tert-butylate 、 溴 、 三苯基膦 作用下， 以 乙醚 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 11.5h， 生成 (3S)-(-)-1-methylenedispiro[2.0.2.1]heptane
  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：

  C-((1R,4aS,10aR)-7-Isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydro-phenanthren-1-yl)-methylamine; compound with (1S,3R)-dispiro[2.0.2.1]heptane-1-carboxylic acid 在 sodium hydroxide 作用下， 以 乙醚 为溶剂， 以84%的产率得到(1S,3R)-(+)-dispiro[2.0.2.1]heptane-1-carboxylic acid
  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

文献信息

• Eaton, Philip E.; Lukin, Kirill A., Journal of the American Chemical Society, 1993, vol. 115, # 24, p. 11370 - 11375
  作者：Eaton, Philip E.、Lukin, Kirill A.

  DOI：——

  日期：——