(R)-pinacol(1-(p-methylphenyl)ethyl)boronate | 257298-94-5

• 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: (R)-pinacol(1-(p-methylphenyl)ethyl)boronate
• 英文别名: (R)-2-(1-(4-methylphenyl)ethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane；(R)-4,4,5,5-tetramethyl-2-(1-(p-tolyl)ethyl)-1,3,2-dioxaborolane；4,4,5,5-Tetramethyl-2-[(1R)-1-(4-methylphenyl)ethyl]-1,3,2-dioxaborolane
• CAS: 257298-94-5
• 化学式: C₁₅H₂₃BO₂
• 分子量: 246.157
• InChiKey: QOLQDMWLBSUIRW-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.73
• 重原子数：
  18
• 可旋转键数：
  2
• 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：

  (R)-pinacol(1-(p-methylphenyl)ethyl)boronate 在 sodium chlorite 、 dipotassium hydrogenphosphate 、 正丁基锂 、 2-甲基-2-丁烯 、 dimethyl sulfide borane 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 叔丁醇 为溶剂， 反应 24.17h， 生成 (R)-2-p-tolylpropan-1-ol
  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：

  Alpha-甲基苯乙烯 、 频哪醇 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl 、 儿萘酚硼烷 作用下， 以 乙二醇二甲醚 为溶剂， 反应 7.0h， 以65%的产率得到(R)-pinacol(1-(p-methylphenyl)ethyl)boronate
  参考文献：
  名称：

  Imao, Daisuke; Glasspoole, Ben W.; Laberge, Veronique S., Journal of the American Chemical Society, 2009, vol. 131, p. 5024 - 5025

  摘要：

  DOI：

文献信息

• Highly Regio- and Enantioselective Copper-Catalyzed Hydroboration of Styrenes
  作者：Dongwan Noh、Heesung Chea、Junghwan Ju、Jaesook Yun

  DOI：10.1002/anie.200902015

  日期：2009.8.3

  An existing challenge is the development of efficient regioselective catalytic systems that are compatible with stable hydroboration reagents and can be rendered enantioselective by the use of nonracemic ligands. Copper(I) complexes with chelating phosphines catalyzed the regio‐ and enantioselective hydroboration of styrenes with pinacolborane (PinBH) at room temperature to afford the corresponding

  现有的挑战是开发与稳定的硼氢化试剂兼容并可以通过使用非外消旋配体使其对映选择性的有效的区域选择性催化体系。在室温下，具有螯合膦的铜（I）配合物催化了频哪醇硼烷（PinBH）对苯乙烯的区域和对映选择性硼氢化反应，从而提供了相应的支链硼酸酯（请参见示例）。
• Nickel-Catalyzed Enantioselective Hydroboration of Vinylarenes
  作者：Hai N. Tran、Levi M. Stanley

  DOI：10.1021/acs.orglett.1c04073

  日期：2022.1.14

  The enantioselective hydroboration of vinylarenes catalyzed by a chiral, nonracemic nickel catalyst is presented as a facile method for generating chiral benzylic boronate esters. Various vinylarenes react with bis(pinacolato)diboron (B2pin2) in the presence of MeOH as a hydride source to form chiral boronate esters in up to 92% yield with up to 94% ee. The use of anhydrous Me4NF to activate B2pin2

  由手性非外消旋镍催化剂催化的乙烯基芳烃的对映选择性硼氢化反应是一种生成手性苯甲基硼酸酯的简便方法。在作为氢化物源的 MeOH 存在下，各种乙烯基芳烃与双（频哪醇）二硼（B 2 pin 2）反应形成手性硼酸酯，产率高达 92%，ee 高达 94%。使用无水 Me 4 NF 激活 B 2 pin 2对于确保快速金属转移以实现高对映选择性至关重要。
• Enantioselective Hydroboration of Styrenes with Markovnikov Selectivity Catalyzed by a Rhodium(I)-NHC Complex
  作者：Kartick Dey、Zeqing Chen、Natalia Fridman、Graham de Ruiter

  DOI：10.1021/acs.organomet.4c00002

  日期：2024.4.22

  developing field where N-heterocyclic carbenes (NHCs) are making increasingly more impact. Herein, we report the synthesis and characterization of carbene-oxazoline containing proligands that exhibit two chiral centers. The corresponding rhodium(I) complexes show excellent activity toward the asymmetric hydroboration of styrenes, which occurs with good regio– and enantioselectivity (up to 96% ee). The

  无膦配体的不对称催化是一个快速发展的领域，其中 N-杂环卡宾 (NHC) 的影响力越来越大。在此，我们报告了含有具有两个手性中心的卡宾-恶唑啉配体的合成和表征。相应的铑(I)配合物对苯乙烯的不对称硼氢化反应表现出优异的活性，并且具有良好的区域选择性和对映选择性（高达 96% ee）。随后氧化所得硼酸酯，并以中等至良好的收率（高达 75%）分离出相应的手性醇。总体而言，硼氢化反应在环境条件下（CH 2 Cl 2；25 °C）发生，与各种官能团相容，并且可以轻松地从相应的烯烃获得手性仲醇。
• Imao, Daisuke; Glasspoole, Ben W.; Laberge, Veronique S., Journal of the American Chemical Society, 2009, vol. 131, p. 5024 - 5025
  作者：Imao, Daisuke、Glasspoole, Ben W.、Laberge, Veronique S.、Crudden, Cathleen M.

  DOI：——

  日期：——
• 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.