(1S,2S,5R,7S,9R)-5-acetyl-3,3,10,10-tetramethyl-4,6-dioxatricyclo[7.1.1.02,7]undecane | 1004540-81-1

• 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: (1S,2S,5R,7S,9R)-5-acetyl-3,3,10,10-tetramethyl-4,6-dioxatricyclo[7.1.1.02,7]undecane
• 英文别名: (1S,2S,5R,7S,9R)-5-acetyl-3,3,10,10-tetramethyl-4,6-dioxatricyclo[7.1.1.0^2,7]undecane
• CAS: 1004540-81-1
• 化学式: C₁₅H₂₄O₃
• 分子量: 252.354
• InChiKey: PDQGKKWHUOOWTA-MOLYVOAJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.78
• 重原子数：
  18.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (1S,2S,5R,7S,9R)-5-acetyl-3,3,10,10-tetramethyl-4,6-dioxatricyclo[7.1.1.02,7]undecane 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 3.0h， 以95%的产率得到(1S,7S,9R)-5-(1'-hydroxyeth-1'-yl)-3,3,10,10-tetramethyl-4,6-dioxatricyclo[7.1.1.0^2,7]undecane
  参考文献：
  名称：

  Nucleophilic additions on acetyldioxanes derived from (−)-(1 R )-myrtenal used as chiral auxiliaries: substituent effects on the stereochemical outcome

  摘要：

  The synthesis of acetyldioxanes 4 and 9a starting from (-)-(1R)-myrtenal is described. The products were treated with a representative series of nucleophilic reagents (RMgX, RLi, NaBH4 and LiAlH4) to assess the effect of the substituent at C-3 on the stereochemical outcome. It was observed that the nucleophiles preferred the re -face of the C=O group when the equatorial substituent at C-3 was a methyl group, whereas a phenyl group at the same position induced the addition through the si-face, thus allowing access to either desired stereochemistry of a final product. This behavior suggests that the formation of the expected Cram-chelated coordination complex takes a coplanar orientation with the C-3 equatorial substituent. Moreover, Grignard reagents were the most stereoselective nucleophiles. The stereochemistry of the addition was established by X-ray diffraction and chemical correlation. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2017.07.008
• 作为产物：
  描述：

  (1S,2S,3S)-2-(1-hydroxy-1-methylethyl)-6,6-dimethylbicyclo[3.1.1]heptan-3-ol 、 1,1-二甲氧基丙酮 在 camphor-10-sulfonic acid 作用下， 以 四氯化碳 、 苯 为溶剂， 反应 72.0h， 以45%的产率得到(1S,2S,5R,7S,9R)-5-acetyl-3,3,10,10-tetramethyl-4,6-dioxatricyclo[7.1.1.02,7]undecane
  参考文献：
  名称：

  New 2-acyl-1,3-dioxane derivatives from (1R)-(−)-myrtenal: stereochemical effect on their relative ability as chiral auxiliaries

  摘要：

  Four 3,10-pinanediol derivatives 1a-d, prepared in 50-72% global yields from (IR)-(-)-myrtenal 2, were treated with (RO)(2)CHCOR3 (R-3 = CH3, Ph) to afford 2-acyl-1,3-dioxanes 3a-f. The latter were submitted to nucleophilic additions using several Grignard reagents to mainly afford carbinols generated by re diastereofacial attack (85-99% yield, >= 88:12 dr). The lowest diastereoselectivity was observed when PhLi or hydrides were used as nucleophiles. Only an equatorial substituent at C-3 modifies the diastereoselectivity of the nucleophilic additions. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2007.10.047