2-((R)-1-Chloro-2-phenyl-propyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane | 257298-97-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 2-((R)-1-Chloro-2-phenyl-propyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane
• 英文别名: 2-[(2R)-1-chloro-2-phenylpropyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 257298-97-8
• 化学式: C₁₅H₂₂BClO₂
• 分子量: 280.602
• InChiKey: QLVWQIPWIWNXEJ-JTDNENJMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.03
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  2-((R)-1-Chloro-2-phenyl-propyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane 在 sodium chlorite 、 dipotassium hydrogenphosphate 、 2-甲基-2-丁烯 作用下， 以 叔丁醇 为溶剂， 反应 24.0h， 生成 (R)-(-)-2-苯基丙酸
  参考文献：
  名称：

  Catalytic Asymmetric Hydrocarboxylation and Hydrohydroxymethylation. A Two-Step Approach to the Enantioselective Functionalization of Vinylarenes

  摘要：

  A method for the catalytic asymmetric hydrocarboxylation and hydrohydroxymethylation of vinylarenes is reported. By separating the step in which asymmetry is installed from the one where carbon-carbon bond formation takes place, a highly enantioselective and regioselective synthesis of Ibuprofen and its analogs is achieved. Stereochemistry is installed via an enantioselective hydroboration reaction, catalyzed by cationic rhodium BINAP complexes, and the homologation is carried out with halomethyllithium reagents. If CH2Cl2/n-BuLi is used as the homologating reagent, carboxylic acids are produced after oxidation. On the other hand, if CH2ClBr is used in combination with n-BuLi, the corresponding primary alcohol is produced. This latter transformation represents a previously unknown asymmetric hydrohydroxymethylation reaction. In both cases, complete retention of stereochemistry is observed, yielding products in up to 97% ee. Superior results are obtained if the initially formed catecholate is converted into a pinacolate prior to homologation.

  DOI：

  10.1021/jo9914216
• 作为产物：
  描述：

  频哪醇 、 alkaline earth salt of/the/ methylsulfuric acid 在 正丁基锂 、 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl 、 儿萘酚硼烷 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 正己烷 为溶剂， 反应 0.67h， 生成 2-((R)-1-Chloro-2-phenyl-propyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane
  参考文献：
  名称：

  Catalytic Asymmetric Hydrocarboxylation and Hydrohydroxymethylation. A Two-Step Approach to the Enantioselective Functionalization of Vinylarenes

  摘要：

  A method for the catalytic asymmetric hydrocarboxylation and hydrohydroxymethylation of vinylarenes is reported. By separating the step in which asymmetry is installed from the one where carbon-carbon bond formation takes place, a highly enantioselective and regioselective synthesis of Ibuprofen and its analogs is achieved. Stereochemistry is installed via an enantioselective hydroboration reaction, catalyzed by cationic rhodium BINAP complexes, and the homologation is carried out with halomethyllithium reagents. If CH2Cl2/n-BuLi is used as the homologating reagent, carboxylic acids are produced after oxidation. On the other hand, if CH2ClBr is used in combination with n-BuLi, the corresponding primary alcohol is produced. This latter transformation represents a previously unknown asymmetric hydrohydroxymethylation reaction. In both cases, complete retention of stereochemistry is observed, yielding products in up to 97% ee. Superior results are obtained if the initially formed catecholate is converted into a pinacolate prior to homologation.

  DOI：

  10.1021/jo9914216