[(1S,3R)-4-methylenespiropent-1-yl]methyl acetate | 321857-31-2

• 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)-4-methylenespiropent-1-yl]methyl acetate
• 英文别名: [(1S,3R)-4-methylenespiropentyl]methyl acetate；[(3R,5S)-2-methylidenespiro[2.2]pentan-5-yl]methyl acetate
• CAS: 321857-31-2
• 化学式: C₉H₁₂O₂
• 分子量: 152.193
• InChiKey: LJLSBWSYNXGYKN-RKDXNWHRSA-N

物化性质

• 沸点：
  193.2±9.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [(1S,3R)-4-methylenespiropent-1-yl]methyl acetate 在 氢氧化钾 、 正丁基锂 、 硫酸 、 苄基三乙基氯化铵 、 diethylzinc 、 4-甲基苯磺酸吡啶 、 三氟乙酸 、 copper dichloride 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 11.5h， 生成 (1S,3R,4R,5S,6S,7R,8R,9S)-(9-hydroxymethylhexaspiro[2.0.0.0.0.0.2.1.1.1.1.1]pentadec-1-yl)methanol
  参考文献：
  名称：

  对映体纯的高级[n-2]三角烷基二甲醇衍生物和[n]三角烷烃（n> / = 7）的收敛途径。

  摘要：

  DOI：

  10.1002/anie.200461166
• 作为产物：
  描述：

  乙酸乙烯酯 、 (rac-4-methylenespiropentyl)methanol 在 Lipase PS 作用下， 以 乙醚 为溶剂， 反应 12.0h， 生成 (1R,3S)-4-methylenespiropent-1-ylmethanol 、 [(1S,3R)-4-methylenespiropent-1-yl]methyl acetate
  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

• Syntheses and Properties of Enantiomerically Pure Higher (n ≥ 7) [n−2]Triangulanedimethanols and σ-[n]Helicenes
  作者：Armin de Meijere、Alexander F. Khlebnikov、Sergei I. Kozhushkov、Dmitrii S. Yufit、Olga V. Chetina、Judith A. K. Howard、Takuya Kurahashi、Kazutoshi Miyazawa、Daniel Frank、Peter R. Schreiner、B. Christopher Rinderspacher、Mari Fujisawa、Chiyo Yamamoto、Yoshio Okamoto

  DOI：10.1002/chem.200600111

  日期：2006.7.24

  lower members (n=4, 5) of the sigma-[n]helicenes. For the higher ones (n=7, 9, 15) the computed specific rotations turn out increasingly larger than the experimental values. The remarkable increase of the specific rotation with an increasing number of three-membered rings is proportional neither to the molecular weight nor to the number of cyclopropane rings in these sigma-[n]helicenes.

  （P）-（+）-Hexaspiro [2.0.0.0。0.0.2.1.1.1.1.1]十五烷[（P）-17]以及（M）-（-）-和（P）-（+）-八倍体[2.0.0.0.0.0.0.0.2.1.1.1。 1.1.1.1]从外消旋THP保护的（亚甲基环丙基）甲醇6开始制备[[M]-和（P）-25]对映体纯的直链[7]-和[9]三角烷的壬二烷[6]。所有重要的中间体以及关键中间体的绝对构型均通过X射线晶体结构分析确定。对n = 7、9的对映体纯线性[n]三角烷酮的这种新的收敛方法也已在针对[15]三角烷的两个变体中进行了测试。新制备的化合物的一些最突出和出乎意料的特征是二醇（P）-14，（E）-（3S，3'S，4S，4'S，5R，5'R）-的自组装显着模式21，（P）-（+）-22，和（E）-31处于固态，通过分子间氢键的构架，取决于各自的结构，导致纳米管-[（P）-14，（P）-（+）-22和（E）-31
• A Novel Type of Chiral Triangulane-Based Diphosphane Ligands for Transition Metals
  作者：Alexander F. Khlebnikov、Sergei I. Kozhushkov、Dmitry S. Yufit、Heiko Schill、Michael Reggelin、Volker Spohr、Armin de Meijere

  DOI：10.1002/ejoc.201101715

  日期：2012.3

  backbone has been elaborated and executed for several representative enantiomerically pure ligands. Thus,(1R,3S,4S)-1,4-bis[(diphenylphosphanyl)methyl]spiro[2.2]pentane [(1R,3S,4S)-24·(BH3)2], [(1R,3R,4S)-4-(diphenylphosphanyl)methylspiro[2.2]pentan-1-yl]diphenylphosphane [(1R,3R,4S)-27·(BH3)2], [(1R,3R,4S,5R)-5-(diphenylphosphanyl)methyldispiro[2.0.2.1]heptan-1-yl]diphenylphosphane [(1R,3R,4S,5R)-30·(BH3)2]

  一种用于合成具有刚性三角骨架的轴向和螺旋手性双齿二膦配体的新原创策略已被阐述并用于几种代表性的对映体纯配体。因此，(1R,3S,4S)-1,4-双[(二苯基膦酰基)甲基]螺[2.2]戊烷[(1R,3S,4S)-24·(BH3)2]，[(1R,3R,4S) )-4-(二苯基膦基)甲基螺[2.2]戊-1-基]二苯基膦[(1R,3R,4S)-27·( )2], [(1R,3R,4S,5R)-5-(二苯基膦基)甲基二螺[2.0.2.1]庚烷-1-基]二苯基膦[(1R,3R,4S,5R)-30·( )2], (1S,3S,4S)-1,4-双(二苯基膦基)螺戊烷[(1R,3S,4S)-35·( )2], (1S,3S,4S)-1,4-双(二苯基膦酰基)螺戊烷[(1S,3S,4S)-35·( )2] , (1S,3S,4S)-1,4-双(二苯基膦酰基)螺戊烷[(1R,3R,4S)-35·( )2]，和(1R
• Miyazawa; Yufit; Howard, European Journal of Organic Chemistry, 2000, # 24, p. 4109 - 4117
  作者：Miyazawa、Yufit、Howard、De Meijere

  DOI：——

  日期：——