(1S,2R,4R)-1,7,7-trimethyl-4'-methylenedihydro-3'H-spiro[bicyclo[2.2.1]heptane-2,2'-furan]-3-one | 960216-94-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: (1S,2R,4R)-1,7,7-trimethyl-4'-methylenedihydro-3'H-spiro[bicyclo[2.2.1]heptane-2,2'-furan]-3-one
• CAS: 960216-94-8
• 化学式: C₁₄H₂₀O₂
• 分子量: 220.312
• InChiKey: LMKWPFRLBQIRIX-BPNCWPANSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.73
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (1S,2R,4R)-1,7,7-trimethyl-4'-methylenedihydro-3'H-spiro[bicyclo[2.2.1]heptane-2,2'-furan]-3-one 、 1,2,4,5-四嗪-3,6-二羧酸二甲酯 以 甲苯 为溶剂， 反应 3.0h， 以77%的产率得到dimethyl (6R,9R,11R,14S)-11:14-isopropylidene-14-methyl-10-oxo-2,3-diaza-8-oxadispiro[5.1.5.2]pentadeca-1,4-diene-1,4-dicarboxylate
  参考文献：
  名称：

  Stereoselective [4+2] cycloadditions of tetrazines to 3-oxo- and 3-arylimino-4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furans]

  摘要：

  Stereo selective inverse-demand [4+2] cycloadditions of 3,6-bis(pyridin-2-yl)-1,2,4,5-tetrazine and dimethyl 1,2,4,5-tetrazine3,6-dicarboxylate to 4'-methylenedihydro-3'H-spiro[bicyclo[2.2.1]heptane-2,2'-furans] and 4'-methylene-1'-(4-nitrophenyl)spiro[bicyclo(2.2.1]heptane-3,2'-pyrrolidine] were studied. Cycloadditions took place stereoselectively at the exocyclic C=C double bonds to give novel 11: 14-isopropylidene-14-methyl-2,3-diaza-8-oxadi spi to [5.1.5.2]pentadecane and 11: 14-isopropylidene-11-methyl-2,3,8-triazadispiro[5.1.5.2]pentadecane derivatives in 50-98% de. The structures of the novel dispiro compounds were determined by NMR techniques, NOESY spectroscopy and X-ray diffraction. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2007.11.012
• 作为产物：
  描述：

  (1S,4R)-1,7,7-trimethyl-3-(phenylimino)bicyclo[2.2.1]heptan-2-one 在 palladium diacetate 盐酸 、 三异丙基亚磷酸酯 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 反应 28.0h， 生成 (1S,2R,4R)-1,7,7-trimethyl-4'-methylenedihydro-3'H-spiro[bicyclo[2.2.1]heptane-2,2'-furan]-3-one
  参考文献：
  名称：

  经由三亚甲基甲烷向（1 S，3 EZ，4 R）-3-arylimino-1,7,7-的立体选择性环加成反应合成螺[bicyclo [2.2.1]庚烷-2,2'-呋喃] -3-胺三甲基双环[2.2.1]庚烷-2-酮

  摘要：

  三亚甲基甲烷（TMM）的立体选择性[3 + 2]环加成与（1 S，3 EZ，4 R）-3-芳基-1,7,7-三甲基双环[2.2.1]庚烷-的环外CO和CN双键2-one给出了相应的螺[双环[2.2.1]庚烷-2,2'-呋喃]和螺[双环[2.2.1]庚烷-3,2'-吡咯烷]衍生物。这些环加合物中CN或CO键的进一步立体选择性还原提供了新的手性胺，二胺和新的氨基醇。的CN双键的所有环加成和减少发生在从较少受阻内的（1 -面小号，3 EZ，4 - [R）-3-芳基氨基-1,7,7-三甲基双环[2.2.1]庚基-2-酮，因此以100％的de给出相应的产物。通过NMR，NOESY光谱和通过X射线衍射确定结构。

  DOI：

  10.1016/j.tetasy.2007.09.018

文献信息

• Synthesis of novel C2-symmetric 1,3-bis{(1S,2R,3S,4R)-1,7,7-trimethyl-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-yl}benzoimidazolium tetrafluoroborates
  作者：Uroš Grošelj、Anton Meden、Branko Stanovnik、Jurij Svete

  DOI：10.1016/j.tetasy.2008.01.005

  日期：2008.2

  Two new C-2-symmetric benzoimidazolium tetrafluoroborates 19 and 20 were prepared from (1S)-(+)-camphorquinone 1 in seven and eight steps, respectively. Thus, N-1-((1S,2R,3S,4R)-1,7,7-trimethyl-4'-methylenedihydro-3'H-spiro[bicyclo[2.2.1]heptane-2,2'-furan]-3-yl)benzene-1.2-diamine 11, available in three steps from 1, was first condensed with 1 to afford amino imines 12 and 13/13'. [3 + 2] Cycloaddition of trimethylenemethane (TMM) to 12 or 13/13' gave cycloadduct 17, which was successfully reduced to diamine 4 using NaCNBH3. Catalytic hydrogenation of methylene groups of 4 gave the methyl analogue 18. Finally, cyclization of diamines 4 and 18 with triethyl orthoformate furnished the desired C-2-symmetric benzoimidazolium tetrafluoroborates 19 and 20, respectively. The structures were determined by NMR techniques, NOESY spectroscopy, and X-ray diffraction. (C) 2008 Elsevier Ltd. All rights reserved.