cis-(R)-1-(5-hydroxycyclooctanyl)benzyl alcohol | 959902-82-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: cis-(R)-1-(5-hydroxycyclooctanyl)benzyl alcohol
• 英文别名: cis-(R)-1-(5-hydroxycyclooctanyl)-1-phenylmethanol
• CAS: 959902-82-0
• 化学式: C₁₅H₂₂O₂
• 分子量: 234.338
• InChiKey: TYUQHSHEWRRAEW-ZNMIVQPWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.05
• 重原子数：
  17.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  40.46
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  (1S,3S,4R)-2-benzyl-3-[(1S,4R)-7,7-dimethyl-2-oxobicyclo[2.2.1]hept-1-yl]-2-thioniabicyclo[2.2.1]heptane tetrafluoroborate 、 B-hexynyl-9-borabicyclo[3.3.1]nonane 在 lithium hexamethyldisilazane 、 sodium hydroxide 、 双氧水 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.0h， 以97%的产率得到cis-(R)-1-(5-hydroxycyclooctanyl)benzyl alcohol
  参考文献：
  名称：

  Asymmetric Sulfur Ylide Reactions with Boranes:  Scope and Limitations, Mechanism and Understanding

  摘要：

  The reactions of aryl-stabilized sulfur ylides with organoboranes has been studied under a variety of conditions. At 5 or -78 degrees C, the reaction with Et3B gave a mixture of the first and second homologation products, but at -100 degrees C, only the first homologation product was obtained even with just 1.1 equiv of Et3B. Under these optimized conditions, the chiral sulfur ylides (derived from camphor sulfonic acid) with different aryl groups were reacted with Et3B to give the corresponding alcohols (95-98% yield, 96-98% ee) and amines (74-77% yield, > 98% ee). The origin of the high enantioselectivity is discussed. The use of nonsymmetrical 9-BBN derivatives was also explored. It was found that whereas primary alkyl substituents gave mixtures of products derived from competing migration of the boron substituent and the boracycle, all other groups resulted in either exclusive migration of the boron substituent (Ph, hexenyl, i-Pr) or exclusive migration of the boracycle (hexynyl, cyclopropyl). The factors responsible for the outcome of the reactions involving a hindered (i-Pr) and an unhindered (propynyl) substituent were studied by DFT calculations. This revealed that, in the case of an unhindered substituent, the conformation of the ate complex is the dominant factor whereas, in the case of a hindered substituent, the barriers to interconversion between the conformers of the ate complex and subsequent migration control the outcome of the reaction.

  DOI：

  10.1021/ja074110i