N¹-{(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 | 960216-98-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: N¹-{(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
• 英文别名: N'-((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；2-N-[(1R,2S,3R,4S)-4,7,7-trimethyl-4'-methylidenespiro[bicyclo[2.2.1]heptane-3,2'-oxolane]-2-yl]benzene-1,2-diamine
• CAS: 960216-98-2
• 化学式: C₂₀H₂₈N₂O
• 分子量: 312.455
• InChiKey: GVHDEBQJJAFDKD-HSCHXYMDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  47.3
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  DL-camphorquinone 、 N¹-{(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 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以31%的产率得到N1-[(1S,3E,4R)-2-oxo-1,7,7-trimethylbicyclo[2.2.1]hept-3-ylidene]-N2-{(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
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1016/j.tetasy.2008.01.005
• 作为产物：
  描述：

  2-nitro-N-{(1S,2R,3E,4R)-1,7,7-trimethyl-4'-methylenedihydro-3'H-spiro[bicyclo[2.2.1]heptane-2,2'-furan]-3-ylidene}aniline 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以63%的产率得到N¹-{(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
  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 spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-amines via stereoselective cycloadditions of trimethylenemethane to (1S,3EZ,4R)-3-arylimino-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ones
  作者：Uroš Grošelj、Anton Meden、Branko Stanovnik、Jurij Svete

  DOI：10.1016/j.tetasy.2007.09.018

  日期：2007.9

  7,7-trimethylbicyclo[2.2.1]heptan-2-ones gave the corresponding spiro[bicyclo[2.2.1]heptane-2,2′-furan] and spiro[bicyclo[2.2.1]heptane-3,2′-pyrrolidine] derivatives. Further stereoselective reductions of the CN or CO bond in these cycloadducts furnished new chiral amines, diamines, and a new aminoalcohol. All cycloadditions and reductions of the CN double bonds took place from the less hindered endo-face

  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。
• 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.