N¹,N²-bis{(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 | 1016546-21-6

• 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,N²-bis{(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: 1-N,2-N-bis[(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: 1016546-21-6
• 化学式: C₃₄H₄₈N₂O₂
• 分子量: 516.767
• InChiKey: KZZJCTXYACTNLQ-HUKLWGETSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  38
• 可旋转键数：
  4
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  42.5
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N¹,N²-bis{(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 、 原甲酸三乙酯 在 甲酸 、 ammonium tetrafluoroborate 作用下， 反应 3.0h， 以61%的产率得到1,3-bis{(1S,2R,3S,4R)-1,7,7-trimethyl-4'-methylenedihydro-3'H-spiro[bicyclo[2.2.1]heptane-2,2'-furan]-3-yl}-1H-benzo[d]imidazol-3-ium tetrafluoroborate
  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：

  N1-{(1S,2R,3S,4R)-1,7,7-trimethyl-4'-methylenedihydro-3'H-spiro[bicyclo[2.2.1]heptane-2,2'-furan]-3-yl}-N2-{(1S,2R,3E,4R)-1,7,7-trimethyl-4'-methylenedihydro-3'H-spiro[bicyclo[2.2.1]heptane-2,2'-furan]-3-ylidene}benzene-1,2-diamine 在 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 反应 20.0h， 以88%的产率得到N¹,N²-bis{(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

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.