(S)-pinacol(1-(p-isobutylphenyl)ethyl)boronate

• 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: (S)-pinacol(1-(p-isobutylphenyl)ethyl)boronate
• 英文别名: 2-(1-(4-isobutylphenyl)ethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane；4,4,5,5-tetramethyl-2-[(1S)-1-[4-(2-methylpropyl)phenyl]ethyl]-1,3,2-dioxaborolane
• 化学式: C₁₈H₂₉BO₂
• 分子量: 288.238
• InChiKey: GUQYKKMFZKYRTQ-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.62
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 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)-pinacol(1-(p-isobutylphenyl)ethyl)boronate 在 sodium chlorite 、 dipotassium hydrogenphosphate 、 正丁基锂 、 2-甲基-2-丁烯 作用下， 以 四氢呋喃 、 正己烷 、 叔丁醇 为溶剂， 反应 24.17h， 生成 (S)-(+)-布洛芬
  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 、 对异丁基苯乙烯 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 儿萘酚硼烷 作用下， 以 乙二醇二甲醚 为溶剂， 反应 8.0h， 生成 (S)-pinacol(1-(p-isobutylphenyl)ethyl)boronate
  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

文献信息

• Catalytic Asymmetric Hydrocarboxylation and Hydrohydroxymethylation. A Two-Step Approach to the Enantioselective Functionalization of Vinylarenes
  作者：Austin Chen、Li Ren、Cathleen M. Crudden

  DOI：10.1021/jo9914216

  日期：1999.12.1

  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.