2-[(2S)-2-(4-chlorophenyl)propyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 257299-05-1

• 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: 2-[(2S)-2-(4-chlorophenyl)propyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: (S)-2-(2-(4-chlorophenyl)propyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 257299-05-1
• 化学式: C₁₅H₂₂BClO₂
• 分子量: 280.602
• InChiKey: OOXHOIYQZGJZPO-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.54
• 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-[(2S)-2-(4-chlorophenyl)propyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 sodium hydroxide 、 双氧水 作用下， 以 甲醇 为溶剂， 生成 (R)-2-(4-chlorophenyl)-propan-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：

  4-氯苯乙烯 、 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 6.0h， 生成 2-[(2S)-2-(4-chlorophenyl)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

文献信息

• Cobalt-Catalyzed Enantioselective Hydroboration of 1,1-Disubstituted Aryl Alkenes
  作者：Lei Zhang、Ziqing Zuo、Xiaolong Wan、Zheng Huang

  DOI：10.1021/ja5093908

  日期：2014.11.5

  We report the synthesis of cobalt complexes of novel iminopyridine-oxazoline (IPO) ligands and their application to the asymmetric hydroboration of 1,1-disubstituted aryl alkenes. The new catalysts afforded α-alkyl-β-pinacolatoboranes with exclusive regioselectivity in high yields with up to 99.5% ee. Furthermore, we have applied this method to an efficient synthesis of naproxen.

  我们报告了新型亚氨基吡啶-恶唑啉 (IPO) 配体的钴配合物的合成及其在 1,1-二取代芳基烯烃的不对称硼氢化中的应用。新催化剂以高产率提供了具有独特区域选择性的 α-烷基-β-频哪醇硼烷，ee 高达 99.5%。此外，我们已将此方法应用于萘普生的有效合成。
• Highly regio- and enantioselective catalytic asymmetric hydroboration of α-substituted styrenyl derivatives
  作者：Clément Mazet、David Gérard

  DOI：10.1039/c0cc01547d

  日期：——

  The catalytic asymmetric hydroboration of a variety of 1,1-disubstituted olefins has been achieved with excellent yields, perfect regioselectivity and in some cases, high levels of enantioselectivity using readily accessible iridium catalyst.

  使用容易获得的铱催化剂，已经以优异的收率，完美的区域选择性以及在某些情况下高水平的对映选择性实现了各种1,1-二取代烯烃的催化不对称硼氢化反应。