2-(Cyclopropylmethyl)-1,3,2-dioxaborinane | 1344115-80-5

• 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-(Cyclopropylmethyl)-1,3,2-dioxaborinane
• 英文别名: 2-(cyclopropylmethyl)-1,3,2-dioxaborinane
• CAS: 1344115-80-5
• 化学式: C₇H₁₃BO₂
• 分子量: 139.99
• InChiKey: LESVKFJWIJXFCY-UHFFFAOYSA-N

物化性质

• 沸点：
  177.6±9.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.32
• 重原子数：
  10
• 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：

  正辛醛 、 2-(Cyclopropylmethyl)-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 2.5h， 以95%的产率得到dodec-1-en-5-ol
  参考文献：
  名称：

  Homoallylboration and Homocrotylboration of Aldehydes

  摘要：

  A simple method for addition of homoallylic fragments to aldehydes is described. Cydopropanated allylboration reagents react with aldehydes in the presence of PhBCl2 to give high yields of bishomoallyl alcohols. Cyclopropanated cis- and trans-crotyl reagents afford the corresponding 1,3-anti- and 1,3-syn-methyl-substituted "homocrotylated" alcohols with high selectivity, consistent with a Zimmerman-Traxler transition state. Accordingly, the optically active alpha-substituted reactant affords the E-substituted product in 97:3 er.

  DOI：

  10.1021/ja2048682
• 作为产物：
  描述：

  (cyclopropylmethyl)boronic acid 、 1,3-丙二醇 在 盐酸 作用下， 以 四氢呋喃 、 乙醚 、 水 为溶剂， 反应 4.83h， 以6.08 g的产率得到2-(Cyclopropylmethyl)-1,3,2-dioxaborinane
  参考文献：
  名称：

  Homoallylboration and Homocrotylboration of Aldehydes

  摘要：

  A simple method for addition of homoallylic fragments to aldehydes is described. Cydopropanated allylboration reagents react with aldehydes in the presence of PhBCl2 to give high yields of bishomoallyl alcohols. Cyclopropanated cis- and trans-crotyl reagents afford the corresponding 1,3-anti- and 1,3-syn-methyl-substituted "homocrotylated" alcohols with high selectivity, consistent with a Zimmerman-Traxler transition state. Accordingly, the optically active alpha-substituted reactant affords the E-substituted product in 97:3 er.

  DOI：

  10.1021/ja2048682

文献信息

• Boron Carboxylate Catalysis of Homoallylboration
  作者：Gabrielle J. Dugas、Yu-hong Lam、K. N. Houk、Isaac J. Krauss

  DOI：10.1021/jo500599h

  日期：2014.5.16

  Boron tris(trifluoroacetate) is identified as the first effective catalyst for the homoallyl- and homocrotylboration of aldehydes by cyclopropylcarbinylboronates. NMR spectroscopic studies and theoretical calculations of key intermediates and transition states both suggest that a ligand-exchange mechanism, akin to our previously reported PhBCl2-promoted homoallylations, is operative. Our experimental and theoretical results also suggest that the catalytic activity of boron tris(trifluoroacetate) might originate from more facile catalytic turnover of the trifluoroacetate ligands (in agreement with DFT calculations) or from a lower propensity for formation of off-pathway reservoir intermediates (as observed by H-1 NMR). This work shows that carboxylates are viable catalytic ligands for homoallyl- and homocrotylations of carbonyl compounds and opens the door to the development of catalytic asymmetric versions of this transformation.
• Homoallylboration and Homocrotylboration of Aldehydes
  作者：Wenbo Pei、Isaac J. Krauss

  DOI：10.1021/ja2048682

  日期：2011.11.23

  A simple method for addition of homoallylic fragments to aldehydes is described. Cydopropanated allylboration reagents react with aldehydes in the presence of PhBCl2 to give high yields of bishomoallyl alcohols. Cyclopropanated cis- and trans-crotyl reagents afford the corresponding 1,3-anti- and 1,3-syn-methyl-substituted "homocrotylated" alcohols with high selectivity, consistent with a Zimmerman-Traxler transition state. Accordingly, the optically active alpha-substituted reactant affords the E-substituted product in 97:3 er.