(1R,2R,3S,5R)-2-hydroxymethyl-3-methylamino-6,6-dimethylbicyclo[3.1.1]heptan-2-ol | 1370261-61-2

• 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: (1R,2R,3S,5R)-2-hydroxymethyl-3-methylamino-6,6-dimethylbicyclo[3.1.1]heptan-2-ol
• 英文别名: (1R,2R,3S,5R)-2-(hydroxymethyl)-6,6-dimethyl-3-(methylamino)bicyclo[3.1.1]heptan-2-ol
• CAS: 1370261-61-2
• 化学式: C₁₁H₂₁NO₂
• 分子量: 199.293
• InChiKey: QTYPTNGCMIRLBH-SDNRWEOFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  52.5
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  聚合甲醛 、 (1R,2R,3S,5R)-2-hydroxymethyl-3-methylamino-6,6-dimethylbicyclo[3.1.1]heptan-2-ol 以 乙醚 、 水 为溶剂， 反应 1.0h， 以41%的产率得到[(1R,2R,6S,8R)-5,9,9-triimethyl-3-oxa-5-azatricyclo[6.1.1.0(2,6)]dec-2-yl]methanol
  参考文献：
  名称：

  Stereoselective synthesis of pinane-type tridentate aminodiols and their application in the enantioselective addition of diethylzinc to benzaldehyde

  摘要：

  A library of pinane-based aminodiols were prepared from commercially available (1R)-(-)-myrtenol (-)-1. Compound (-)-1 was transformed into ally! trichloroacetamide (+)-2 via the acetimidate, followed by the Overman rearrangement. In order obtain the aminodiol structure, (+)-2 was subjected to stereoselective dihydroxylation with OsO4, resulting in dihydroxy trichloroacetamide (+)-3. The trichloroacetyl group was removed from (+)-3 with aqueous HCl and the (1R,2R,3S,5R)-3-amino-2-hydroxymethyl-6,6-dimethylbicyclo[3.1.1]heptan-2-ol hydrochloride (-)-4 obtained was transformed to primary, secondary and tertiary aminodiols by reductive amination, N-alkylation of aminodiol (+)-9 and debenzylation of N-benzyl aminodiol (+)-10, respectively. In the reactions of (+)-9 and (+)-14 with formaldehyde, highly regioselective ring closure was observed. In contrast with earlier results, the aminodiols gave pinane-fused oxazolidines (+)-11 and (-)-15. The aminodiols and their oxazolidine derivatives 5-15 were applied as chiral catalysts in the enantioselective addition of diethylzinc to benzaldehyde. The best enantioselectivity was observed in the case of the N-benzyl-substituted derivative (+)-9. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.01.020
• 作为产物：
  描述：

  [(1R,2R,6S,8R)-5-benzyl-9,9-dimethyl-3-oxa-5-azatricyclo[6.1.1.0(2,6)]dec-2-yl]methanol 在 lithium aluminium tetrahydride 、 5%-palladium/activated carbon 、 氢气 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 生成 (1R,2R,3S,5R)-2-hydroxymethyl-3-methylamino-6,6-dimethylbicyclo[3.1.1]heptan-2-ol
  参考文献：
  名称：

  Stereoselective synthesis of pinane-type tridentate aminodiols and their application in the enantioselective addition of diethylzinc to benzaldehyde

  摘要：

  A library of pinane-based aminodiols were prepared from commercially available (1R)-(-)-myrtenol (-)-1. Compound (-)-1 was transformed into ally! trichloroacetamide (+)-2 via the acetimidate, followed by the Overman rearrangement. In order obtain the aminodiol structure, (+)-2 was subjected to stereoselective dihydroxylation with OsO4, resulting in dihydroxy trichloroacetamide (+)-3. The trichloroacetyl group was removed from (+)-3 with aqueous HCl and the (1R,2R,3S,5R)-3-amino-2-hydroxymethyl-6,6-dimethylbicyclo[3.1.1]heptan-2-ol hydrochloride (-)-4 obtained was transformed to primary, secondary and tertiary aminodiols by reductive amination, N-alkylation of aminodiol (+)-9 and debenzylation of N-benzyl aminodiol (+)-10, respectively. In the reactions of (+)-9 and (+)-14 with formaldehyde, highly regioselective ring closure was observed. In contrast with earlier results, the aminodiols gave pinane-fused oxazolidines (+)-11 and (-)-15. The aminodiols and their oxazolidine derivatives 5-15 were applied as chiral catalysts in the enantioselective addition of diethylzinc to benzaldehyde. The best enantioselectivity was observed in the case of the N-benzyl-substituted derivative (+)-9. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.01.020