cis-3-[(1SR)-1-hydroxyethyl]-4-[(1RS)-1-hydroxyethyl]-1,2,3,4-tetramethyl-1-cyclobutene | 845626-85-9

• 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: cis-3-[(1SR)-1-hydroxyethyl]-4-[(1RS)-1-hydroxyethyl]-1,2,3,4-tetramethyl-1-cyclobutene
• 英文别名: (1S)-1-[(1R,4S)-4-[(1R)-1-hydroxyethyl]-1,2,3,4-tetramethylcyclobut-2-en-1-yl]ethanol
• CAS: 845626-85-9
• 化学式: C₁₂H₂₂O₂
• 分子量: 198.305
• InChiKey: SOUCJLRUPBXCMZ-BKUVIOGVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  二氯二甲基硅烷 、 cis-3-[(1SR)-1-hydroxyethyl]-4-[(1RS)-1-hydroxyethyl]-1,2,3,4-tetramethyl-1-cyclobutene 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以60%的产率得到(1α,2α,6α,7α)1,2,4,4,6,7,8,9-octamethyl-3,5-dioxa-4-silabicyclo[5.2.0]-8-nonene
  参考文献：
  名称：

  Nucleophilic addition to 3,4-cis-diacetyl-1,2,3,4-tetramethyl-1-cyclobutene: remarkably fast intramolecular hemiketalization

  摘要：

  Reduction of 3,4-cis-diacetyl-1,2,3,4-tetramethyl-1-cyclobutene 1 with NaBH4 yielding 2-hydroxyoxoianes 2a and 2b with complete diastereoselectivity at the anomeric carbon atom suggests that a highly stereoselective intramolecular hemiketalizaiion process leading to the formation of the 2-hydroxyoxolane unit is much faster than the attack of the second molecule of the nucleophile on the second carbonyl group. Further reduction of 2a at 0 degreesC Lives selectively the meso-diol 3a. Reaction of 1 with MeLi or MeMgBr also involves the participation of the adjacent carbonyl. thereby yielding hydroxyoxolane 5a selectively. A mechanistic rationale is proposed oil the basis of the relative energies of all isomeric hemiketals, 2a-d and 5a and b, (calculated by the PM3 method) and the relative stabilities of the conformers of 1 (calculated by the MM2 method). (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.12.037
• 作为产物：
  描述：

  3,4-diacetyl-1,2,3,4-tetramethylcyclobutene 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 2.0h， 生成 cis-3-[(1SR)-1-hydroxyethyl]-4-[(1RS)-1-hydroxyethyl]-1,2,3,4-tetramethyl-1-cyclobutene
  参考文献：
  名称：

  Nucleophilic addition to 3,4-cis-diacetyl-1,2,3,4-tetramethyl-1-cyclobutene: remarkably fast intramolecular hemiketalization

  摘要：

  Reduction of 3,4-cis-diacetyl-1,2,3,4-tetramethyl-1-cyclobutene 1 with NaBH4 yielding 2-hydroxyoxoianes 2a and 2b with complete diastereoselectivity at the anomeric carbon atom suggests that a highly stereoselective intramolecular hemiketalizaiion process leading to the formation of the 2-hydroxyoxolane unit is much faster than the attack of the second molecule of the nucleophile on the second carbonyl group. Further reduction of 2a at 0 degreesC Lives selectively the meso-diol 3a. Reaction of 1 with MeLi or MeMgBr also involves the participation of the adjacent carbonyl. thereby yielding hydroxyoxolane 5a selectively. A mechanistic rationale is proposed oil the basis of the relative energies of all isomeric hemiketals, 2a-d and 5a and b, (calculated by the PM3 method) and the relative stabilities of the conformers of 1 (calculated by the MM2 method). (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.12.037