2-[[(1R,2R)-2-methylcyclopropyl]methyl]-1,3,2-dioxaborinane | 1417175-94-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: 2-[[(1R,2R)-2-methylcyclopropyl]methyl]-1,3,2-dioxaborinane
• CAS: 1417175-94-0
• 化学式: C₈H₁₅BO₂
• 分子量: 154.017
• InChiKey: QZWCACMPULDCIZ-SFYZADRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.57
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  (S)-2-甲基丁醛 、 2-[[(1R,2R)-2-methylcyclopropyl]methyl]-1,3,2-dioxaborinane 在 二氯苯酚溴酯 、 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 90.0h， 以76%的产率得到(3S,4S,6R)-3,6-dimethyloct-7-en-4-ol
  参考文献：
  名称：

  Enantioselective Homocrotylboration of Aliphatic Aldehydes

  摘要：

  A practical route to optically pure syn-homocrotylation reagents is described, including highly diastereo- and enantioselective preparation of numerous syn-homocrotyl products, as well as several matched mismatched pairs. NMR experiments suggest that the active homocrotylating species is a cyclopropylcarbinyldichloroborane generated by chloride exchange from the PhBCl2 activator. Computational studies support the intermediacy of chloroboranes and suggest that homoallyl/homocrotyl transfers occur through Zimmerman-Traxler transition states.

  DOI：

  10.1021/ja311061n
• 作为产物：
  描述：

  、 1,3-丙二醇 在 sodium periodate 作用下， 以89%的产率得到2-[[(1R,2R)-2-methylcyclopropyl]methyl]-1,3,2-dioxaborinane
  参考文献：
  名称：

  Enantioselective Homocrotylboration of Aliphatic Aldehydes

  摘要：

  A practical route to optically pure syn-homocrotylation reagents is described, including highly diastereo- and enantioselective preparation of numerous syn-homocrotyl products, as well as several matched mismatched pairs. NMR experiments suggest that the active homocrotylating species is a cyclopropylcarbinyldichloroborane generated by chloride exchange from the PhBCl2 activator. Computational studies support the intermediacy of chloroboranes and suggest that homoallyl/homocrotyl transfers occur through Zimmerman-Traxler transition states.

  DOI：

  10.1021/ja311061n

文献信息

• Enantioselective <i>syn</i> and <i>anti</i> Homocrotylation of Aldehydes: Application to the Formal Synthesis of Spongidepsin
  作者：Hongkun Lin、Leiming Tian、Isaac J. Krauss

  DOI：10.1021/jacs.5b08858

  日期：2015.10.14

  Whereas crotylboration has been a useful method for synthesis of stereochemically complex products, we have shown that homocrotylboration can be achieved with cyclopropanated crotylation reagents, and that the stereo-selectivity of the reaction can be predicted by analogous models. This paper presents a full account of this work, including the first examples of asymmetric anti homocrotylation. The scope of this reaction is demonstrated with highly enantioselective homocrotylation of both aliphatic and aromatic aldehydes, as well as double diastereoselection studies. An application of the synthesis of the marine natural product spongidepsin is presented, as well as streamlined syntheses of homocrotylation reagents.
• Enantioselective Homocrotylboration of Aliphatic Aldehydes
  作者：Hongkun Lin、Wenbo Pei、Hao Wang、Kendall N. Houk、Isaac J. Krauss

  DOI：10.1021/ja311061n

  日期：2013.1.9

  A practical route to optically pure syn-homocrotylation reagents is described, including highly diastereo- and enantioselective preparation of numerous syn-homocrotyl products, as well as several matched mismatched pairs. NMR experiments suggest that the active homocrotylating species is a cyclopropylcarbinyldichloroborane generated by chloride exchange from the PhBCl2 activator. Computational studies support the intermediacy of chloroboranes and suggest that homoallyl/homocrotyl transfers occur through Zimmerman-Traxler transition states.