α-<<(2E,6R,7Z)-9-Bromo-7-iodo-2,6-dimethyl-2,7-nonadienyl>oxy>-p-methoxytoluene | 167385-60-6

• 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: α-<<(2E,6R,7Z)-9-Bromo-7-iodo-2,6-dimethyl-2,7-nonadienyl>oxy>-p-methoxytoluene
• 英文别名: 1-[[(2E,6R,7Z)-9-bromo-7-iodo-2,6-dimethylnona-2,7-dienoxy]methyl]-4-methoxybenzene
• CAS: 167385-60-6
• 化学式: C₁₉H₂₆BrIO₂
• 分子量: 493.223
• InChiKey: YEYVXFZFBZBBGC-YLZOTGOWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  23
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  α-<<(2E,6R,7Z)-9-Bromo-7-iodo-2,6-dimethyl-2,7-nonadienyl>oxy>-p-methoxytoluene 在 sodium tetrahydroborate 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 80.5h， 生成 (1R,2R,3R,4R,11S)-4-<(1R,3Z,4S,8E)-1-<(tert-Butyldimethylsiloxy)methyl>-4-iodo-10-<(p-methoxybenzyl)oxy>-5,9-dimethyl-3,8-decadienyl>-11-methyltricyclo<5.4.0.0^2,11>undec-7-en-3-ol
  参考文献：
  名称：

  Studies Directed toward the Total Synthesis of Cerorubenic Acid-III. 4. Exploration of an Organometallic Approach to Construction of the Eastern Sector

  摘要：

  The concept of an intramolecular organometallic approach to the most illustrious member of the cerorubenic acid family is outlined. Alkylation of ketone 2 with the ethyl iodoacetate and conversion of the resultant intermediate into lactone 9 provided a ready means for attaching side chains carrying a vinyl iodide substituent. Arrival at the key iodo ketones was next realized by a three-step sequence involving sodium borohydride reduction, regiocontrolled silylation of the primary hydroxyl group in the diol, and Dess-Martin oxidation. The crucial six-membered cyclization of these intermediates is not favored kinetically, and reductive deiodination was observed, if reaction occurred at all. Attempts to generate vinyl stannanes from these same substrates were also ineffective. The failure of this approach demonstrates the difficulties associated with closure of ring D, a phenomenon that has earlier been observed in the context of other exploratory routes to cerorubenic acid-III.

  DOI：

  10.1021/jo00120a026
• 作为产物：
  描述：

  Methyl (2Z,7E)-3-Iodo-9-<(p-methoxybenzyl)oxy>-4,8-dimethyl-2,7-nonadien-1-ol 在 四溴化碳 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 生成 α-<<(2E,6S,7Z)-9-Bromo-7-iodo-2,6-dimethyl-2,7-nonadienyl>oxy>-p-methoxytoluene 、 α-<<(2E,6R,7Z)-9-Bromo-7-iodo-2,6-dimethyl-2,7-nonadienyl>oxy>-p-methoxytoluene
  参考文献：
  名称：

  Studies Directed toward the Total Synthesis of Cerorubenic Acid-III. 4. Exploration of an Organometallic Approach to Construction of the Eastern Sector

  摘要：

  The concept of an intramolecular organometallic approach to the most illustrious member of the cerorubenic acid family is outlined. Alkylation of ketone 2 with the ethyl iodoacetate and conversion of the resultant intermediate into lactone 9 provided a ready means for attaching side chains carrying a vinyl iodide substituent. Arrival at the key iodo ketones was next realized by a three-step sequence involving sodium borohydride reduction, regiocontrolled silylation of the primary hydroxyl group in the diol, and Dess-Martin oxidation. The crucial six-membered cyclization of these intermediates is not favored kinetically, and reductive deiodination was observed, if reaction occurred at all. Attempts to generate vinyl stannanes from these same substrates were also ineffective. The failure of this approach demonstrates the difficulties associated with closure of ring D, a phenomenon that has earlier been observed in the context of other exploratory routes to cerorubenic acid-III.

  DOI：

  10.1021/jo00120a026