(-)-1-(2-bromophenyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢异喹啉
• 英文名称: (-)-1-(2-bromophenyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline
• 英文别名: (S)-1-(2-bromophenyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline；(1S)-1-(2-bromophenyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline
• 化学式: C₁₇H₁₈BrNO₂
• 分子量: 348.239
• InChiKey: AXOQZSCPPBRDTD-QGZVFWFLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  30.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (-)-1-(2-bromophenyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline 在 氨 、 铜 、 copper(l) chloride 作用下， 70.0 ℃ 、4.5 MPa 条件下， 反应 120.0h， 以82%的产率得到(S)-1-(2-aminophenyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline
  参考文献：
  名称：

  Substituted Isoquinolines by Noyori Transfer Hydrogenation:  Enantioselective Synthesis of Chiral Diamines Containing an Aniline Subunit

  摘要：

  Transfer hydrogenation using the Noyori catalyst 5-Ts is effective for the enantioselective hydrogenation of imines containing fully substituted nitrogen groups (12 or 13). Analogues such as Ile could not be reduced in practical yield, apparently due to product inhibition of the catalyst. Asymmetric transfer hydrogenation of the aniline imine 8a was possible, but required. impractical purity levels for the substrate, and the nitro analogue 7 could not be reduced efficiently. The best results were Obtained with the bromophenyl imine 20, In the case of 20b, the product 21b was formed with 98.7% ee, and the material could be upgraded to >99% ee by crystallization of the hydrochloride salt. Reaction of 21b with NH3 or MeNH2 in the presence of Cu/CuCl gave the chiral anilines 10b or 23b. The latter substance is comparable to the commercially available 1 as a chiral proton donor fog amide enolates and provides access to the hitherto unavailable enantiomeric series.

  DOI：

  10.1021/jo990594s
• 作为产物：
  描述：

  6,7-dimethoxy-1-<(ortho-bromo)phenyl>-3,4-dihydroisoquinoline 在 甲酸 、 RuCl[(1R,2R)-p-TsNCH(C6H5)CH-(C6H5)NH2](η6-benzene) 、 三乙胺 作用下， 以 异丙醇 为溶剂， 反应 16.0h， 以72%的产率得到(-)-1-(2-bromophenyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline
  参考文献：
  名称：

  钌催化的1-芳基取代的二氢异喹啉的不对称转移加氢：获得有价值的手性1-芳基-四氢异喹啉骨架

  摘要：

  给我一个H！再给我一个H！描述了第一个普通的和高对映选择性的Ru催化的广泛的1-芳基取代的1,2,3,4-二氢异喹啉的转移加氢反应。这种原子经济反应在温和的条件下进行，可以快速获得相应的生物学相关的1-芳基-四氢异喹啉衍生物，且收率高，对映选择性高达99％。

  DOI：

  10.1002/anie.201301134

文献信息

• Ruthenium-Catalyzed Asymmetric Transfer Hydrogenation of 1-Aryl-Substituted Dihydroisoquinolines: Access to Valuable Chiral 1-Aryl-Tetrahydroisoquinoline Scaffolds
  作者：Zi Wu、Marc Perez、Michelangelo Scalone、Tahar Ayad、Virginie Ratovelomanana-Vidal

  DOI：10.1002/anie.201301134

  日期：2013.4.26

  Give me an H! Give me another H! The first general and highly enantioselective Ru‐catalyzed transfer hydrogenation of a wide range of 1‐aryl‐substituted 1,2,3,4‐dihydroisoquinolines is described. This atom‐economic reaction proceeds under mild conditions, allowing rapid access to the corresponding biologically relevant 1‐aryl‐tetrahydroisoquinoline derivatives, in high yields and enantioselectivities

  给我一个H！再给我一个H！描述了第一个普通的和高对映选择性的Ru催化的广泛的1-芳基取代的1,2,3,4-二氢异喹啉的转移加氢反应。这种原子经济反应在温和的条件下进行，可以快速获得相应的生物学相关的1-芳基-四氢异喹啉衍生物，且收率高，对映选择性高达99％。
• Substituted Isoquinolines by Noyori Transfer Hydrogenation:  Enantioselective Synthesis of Chiral Diamines Containing an Aniline Subunit
  作者：E. Vedejs、P. Trapencieris、E. Suna

  DOI：10.1021/jo990594s

  日期：1999.9.1

  Transfer hydrogenation using the Noyori catalyst 5-Ts is effective for the enantioselective hydrogenation of imines containing fully substituted nitrogen groups (12 or 13). Analogues such as Ile could not be reduced in practical yield, apparently due to product inhibition of the catalyst. Asymmetric transfer hydrogenation of the aniline imine 8a was possible, but required. impractical purity levels for the substrate, and the nitro analogue 7 could not be reduced efficiently. The best results were Obtained with the bromophenyl imine 20, In the case of 20b, the product 21b was formed with 98.7% ee, and the material could be upgraded to >99% ee by crystallization of the hydrochloride salt. Reaction of 21b with NH3 or MeNH2 in the presence of Cu/CuCl gave the chiral anilines 10b or 23b. The latter substance is comparable to the commercially available 1 as a chiral proton donor fog amide enolates and provides access to the hitherto unavailable enantiomeric series.
• Enantioselective Synthesis of 1-Aryl-Substituted Tetrahydroisoquinolines Through Ru-Catalyzed Asymmetric Transfer Hydrogenation
  作者：Marc Perez、Zi Wu、Michelangelo Scalone、Tahar Ayad、Virginie Ratovelomanana-Vidal

  DOI：10.1002/ejoc.201500951

  日期：2015.9

  A convenient and general asymmetric transfer hydrogenation of a wide array of 1-aryl-3,4-dihydroisoquinoline derivatives using a [RuIICl(η6-benzene)TsDPEN] complex in combination with a 5:2 HCOOH–Et3N azeotropic mixture as a hydrogen source was developed. Under mild reaction conditions, the described catalytic transformation secured a practical synthetic access to the corresponding valuable chiral

  使用 [RuIICl(η6-苯)TsDPEN] 配合物与 5:2 HCOOH-Et3N 共沸混合物作为氢源，方便且通用地对各种 1-芳基-3,4-二氢异喹啉衍生物进行不对称转移氢化已开发。在温和的反应条件下，所描述的催化转化确保了获得相应有价值的手性 1-芳基四氢异喹啉单元的实际合成途径，该单元具有高原子经济性、广泛的底物范围、高分离产率（高达 97%）和良好的对映选择性（高达99% ee)。发现反应的立体化学结果受催化剂结构和底物上存在的取代基的强烈影响。