(1S,3S)-(dispiro[2.0.2.1]hept-1-yl)methanol | 321857-37-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,3S)-(dispiro[2.0.2.1]hept-1-yl)methanol
• 英文别名: [(4S,5S)-dispiro[2.0.24.13]heptan-5-yl]methanol
• CAS: 321857-37-8
• 化学式: C₈H₁₂O
• 分子量: 124.183
• InChiKey: LTKJWYVADOMAGA-SVRRBLITSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1S,3S)-(dispiro[2.0.2.1]hept-1-yl)methanol 在 吡啶 、 potassium tert-butylate 、 溴 、 三苯基膦 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 9.5h， 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：

  (1S,3S)-(dispiro[2.0.2.1]hept-1-yl)methyl acetate 在 硫酸 作用下， 以 甲醇 为溶剂， 以72%的产率得到(1S,3S)-(dispiro[2.0.2.1]hept-1-yl)methanol
  参考文献：
  名称：

  Miyazawa; Yufit; Howard, European Journal of Organic Chemistry, 2000, # 24, p. 4109 - 4117

  摘要：

  DOI：

文献信息

• Optically Active Mesogenic Dispiro[2.0.2.1]Heptane Derivatives and their Unusual Physical Properties
  作者：Kazutoshi Miyazawa、Dietrich Demus、Armin De Meijere

  DOI：10.1080/10587250108024994

  日期：2001.8

  Physical properties. i.e. phase transition temperatures, response times, Ps values, tilt angles. helical twisting powers and helical twisting senses of a series of novel ferroelectric liquid crystalline compounds with non-substituted and halogen-substituted dispiro[2.0.2.1]heptyl moieties in their side chains have been measured, When mixed with an achiral SmC base mixture, the resulting SmC* mixtures containing the novel compounds showed ferroelectricity, and the novel compounds were estimated as useful dopants for ferroelectric liquid crystal mixtures. Further unusual properties were observed with the combinations of the two diastereomeric novel compounds, for example (1S,3R,4S)-4a and (1S,3R,4R)-5a. They showed opposite signs for the Ps and the same sense for the N* helical twisting, which clearly suggests that the direction of the Ps and helical sense of N* must be derived from different origins.
• Miyazawa; Yufit; Howard, European Journal of Organic Chemistry, 2000, # 24, p. 4109 - 4117
  作者：Miyazawa、Yufit、Howard、De Meijere

  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.