14-bromotetradec-1-en-4-ol | 1115861-41-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 14-bromotetradec-1-en-4-ol
• 英文别名: 14-bromo-1-tetradecen-4-ol
• CAS: 1115861-41-0
• 化学式: C₁₄H₂₇BrO
• 分子量: 291.272
• InChiKey: CTNQNNMVTOOSNO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.83
• 重原子数：
  16.0
• 可旋转键数：
  12.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  14-bromotetradec-1-en-4-ol 在 吡啶 、 四丁基氟化铵 、 potassium carbonate 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 113.5h， 生成
  参考文献：
  名称：

  带有牺牲氧化硅桥的大环双环烯烃的开环复分解聚合

  摘要：

  我们开发了一种在双键的 α,β'-位上带有牺牲硅氧基桥的大双环烯烃体系，作为区域选择性开环复分解聚合的新序列定义单体。单体序列信息被植入大环中，而具有较大环张力的小环不仅可以提供窄的多分散性，还可以提供高的区域/立体特异性。

  DOI：

  10.1002/anie.202112526
• 作为产物：
  描述：

  11-溴-1-十一醇 在 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 14-bromotetradec-1-en-4-ol
  参考文献：
  名称：

  带有牺牲氧化硅桥的大环双环烯烃的开环复分解聚合

  摘要：

  我们开发了一种在双键的 α,β'-位上带有牺牲硅氧基桥的大双环烯烃体系，作为区域选择性开环复分解聚合的新序列定义单体。单体序列信息被植入大环中，而具有较大环张力的小环不仅可以提供窄的多分散性，还可以提供高的区域/立体特异性。

  DOI：

  10.1002/anie.202112526

文献信息

• Biomimetic Transannular Oxa-Conjugate Addition Approach to the 2,6-Disubstituted Dihydropyran of Laulimalide Yields an Unprecedented Transannular Oxetane
  作者：Stephen R. Houghton、Laura Furst、Christopher N. Boddy

  DOI：10.1021/jo8023494

  日期：2009.2.20

  2,6-Disubstituted dihydropyrans are a common feature in many bioactive polyketides, including the anticancer marine polyketide laulimalide. While much of the uncharacterized biosynthetic pathway for laulimalide can be confidently postulated, the biosynthetic origins of the trans 2,6-disubstituted dihydropyran cannot. We hypothesize that a transannular oxa-conjugate addition in a macrocyclic laulimalide precursor could be the origin of the 2,6-dihydropyran. To test this hypothesis, we constructed a model containing the key functional groups for oxa-conjugate addition-mediated dihydropyran formation. Under acid-mediated conditions, the model under went regiospecific oxa-conjugate addition producing a stable trans oxetane as the only regioisomer. The desired, more stable dihydropyran was not detected. This unprecedented regiospecificity is unexpected due to the ring strain of the oxetane and the anticipated facile ring opening retro-oxa-conjugate addition. The oxetane is stable to acid and basic conditions, as are a number of literature acyclic oxetanes that could undergo similar retro-oxa-conjugate addition. While the source of the oxetane kinetic stability is yet to be characterized, it may enable general oxetane construction via oxa-conjugate addition. The more stable dihydropyran regioisomer could not be generated due to poor geometrical orbital alignment and hard-soft incompatibility between the hard oxygen nucleophile and the soft activated polyenoate electrophile. These factors disfavor the breaking of conjugation by oxa-conjugate addition. Based on these results we propose that dihydropyran formation does not occur on completed polyketide macrocycles as we had proposed but rather during polyketide biosynthesis on the growing polyketide chain.