3-(7,7-Dimethyl-1,4-dioxa-spiro[4.5]dec-6-yl)-propan-1-ol | 183549-73-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(7,7-Dimethyl-1,4-dioxa-spiro[4.5]dec-6-yl)-propan-1-ol
• 英文别名: 3-(7,7-Dimethyl-1,4-dioxaspiro[4.5]decan-6-yl)propan-1-ol
• CAS: 183549-73-7
• 化学式: C₁₃H₂₄O₃
• 分子量: 228.332
• InChiKey: VYSZBVMHFSFBMQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(7,7-Dimethyl-1,4-dioxa-spiro[4.5]dec-6-yl)-propan-1-ol 在 四丙基高钌酸铵 、 硼酸三甲酯 、 三氯化硼 、 对甲苯磺酸 、 pyridinium chlorochromate 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 2-(2,5,5-trimethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)acetaldehyde
  参考文献：
  名称：

  Studies on the Synthesis of Acanthodoral and Nanaimoal:  Evaluation of Cationic Cyclization Routes

  摘要：

  Intramolecular Lewis acid-promoted reactions of alpha,beta-unsaturated ketone 6 and aldehydes 7 and 8 were examined as potential routes to acanthodoral (1), a structurally interesting natural product. Ketone 6 afforded ene product 22 exclusively, and both 7 and 8 gave mixtures of bicyclic aldehydes 3 and 26 and tricyclic aldehyde 25. The latter most likely results from 7 by intramolecular cyclization of the alkene onto the Lewis acid-activated carbonyl moiety affording carbocation 31 followed by a 1,2-hydride shift and ring closure. Starting from 8, tricyclic aldehyde 25 apparently forms by cyclization to cation 35 and ring closure to cyclobutane 36, followed by ring opening to 31, the same cation as formed in reactions of 7. Nanaimoal (3) results from loss of H+ from 31, and bicyclic aldehyde 26 may be formed in a similar manner or by a concerted ene reaction. The configuration of 25 establishes that the stereochemistry of the initial cyclization to 31 precludes the possible use of this strategy for the synthesis of acanthodoral. However, acid-promoted cyclization of allylic alcohol 23 efficiently gives diene 29 which undergoes selective hydroboration/oxidation to afford nanaimoal.

  DOI：

  10.1021/jo9610568
• 作为产物：
  描述：

  3-(7,7-Dimethyl-1,4-dioxa-spiro[4.5]dec-6-yl)-propionic acid methyl ester 在 lithium aluminium tetrahydride 作用下， 以90%的产率得到3-(7,7-Dimethyl-1,4-dioxa-spiro[4.5]dec-6-yl)-propan-1-ol
  参考文献：
  名称：

  Studies on the Synthesis of Acanthodoral and Nanaimoal:  Evaluation of Cationic Cyclization Routes

  摘要：

  Intramolecular Lewis acid-promoted reactions of alpha,beta-unsaturated ketone 6 and aldehydes 7 and 8 were examined as potential routes to acanthodoral (1), a structurally interesting natural product. Ketone 6 afforded ene product 22 exclusively, and both 7 and 8 gave mixtures of bicyclic aldehydes 3 and 26 and tricyclic aldehyde 25. The latter most likely results from 7 by intramolecular cyclization of the alkene onto the Lewis acid-activated carbonyl moiety affording carbocation 31 followed by a 1,2-hydride shift and ring closure. Starting from 8, tricyclic aldehyde 25 apparently forms by cyclization to cation 35 and ring closure to cyclobutane 36, followed by ring opening to 31, the same cation as formed in reactions of 7. Nanaimoal (3) results from loss of H+ from 31, and bicyclic aldehyde 26 may be formed in a similar manner or by a concerted ene reaction. The configuration of 25 establishes that the stereochemistry of the initial cyclization to 31 precludes the possible use of this strategy for the synthesis of acanthodoral. However, acid-promoted cyclization of allylic alcohol 23 efficiently gives diene 29 which undergoes selective hydroboration/oxidation to afford nanaimoal.

  DOI：

  10.1021/jo9610568