(4,5-二甲氧基-7-甲基-1-萘基)硼酸 | 177971-27-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 中文名称: (4,5-二甲氧基-7-甲基-1-萘基)硼酸
• 中文别名: 硼酸,(4,5-二甲氧基-7-甲基-1-萘基)-(9CI)
• 英文名称: 4,5-dimethoxy-7-methyl-1-naphthyl boronic acid
• 英文别名: [4,5-dimethoxy-7-methyl-1-naphthalenyl]boronic acid；(4,5-Dimethoxy-7-methylnaphthalen-1-yl)boronic acid
• CAS: 177971-27-6
• 化学式: C₁₃H₁₅BO₄
• 分子量: 246.071
• InChiKey: BDRLHLSAUDPNLJ-UHFFFAOYSA-N

物化性质

• 沸点：
  461.9±55.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.85
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4,5-二甲氧基-7-甲基-1-萘基)硼酸 在 palladium on activated charcoal 、 四(三苯基膦)钯 氢气 、 碳酸氢钠 作用下， 以 甲醇 、 二氯甲烷 、 水 、 甲苯 为溶剂， 20.0~110.0 ℃ 、101.33 kPa 条件下， 反应 16.0h， 生成 [(1R),1R*,3R*,5R*]-1,2,3,4-tetrahydro-5-(4,5-dimethoxy-7-methyl-1-naphthalenyl)-1,3-dimethyl-6,8-isoquinolinediol
  参考文献：
  名称：

  Total Synthesis of Michellamines A−C, Korupensamines A−D, and Ancistrobrevine B

  摘要：

  Efficient syntheses of the title compounds have been developed. Several strategies for preparation of each of the naphthalene and tetrahydroisoquinoline (THIQ) portions were developed. Initial attempts to use benzyne plus furan cycloaddition reactions were thwarted by the unfavorable sense of the regiochemical outcome. An interesting annulation reaction of benzynes derived from 2,4-dibromophenol derivatives formed the core of the shortest naphthalene synthesis. An alternative annulation initiated by the addition of a benzylic sulfone anion to methyl crotonate led to an efficient naphthol synthesis amenable to large scale. The THIQ synthesis of Bringmann was used initially and subsequently complemented by a route whose key step involved the opening of N-tosyl-2-methylethyleneimine by a 3,5-dimethoxyphenylcuprate reagent. The results from a variety of aryl cross-coupling reactions are described. Suzuki coupling of the boronic acid derived from the naphthalene moiety with a THIQ-iodide was the most generally effective method for forming the hindered biaryl bond. The korupensamines and ancistrobrevine B were then revealed by deprotection. The oxidative coupling of several 4-aryl-1-naphthols to indigoids (cross ring naphthoquinones) with silver oxide effected the critical dimerization reaction needed to establish the michellamine skeleton. For the perbenzylated precursor, hydrogen over palladium on carbon both reductively bleached the indigoid and hydrogenolyzed the benzyl ethers and amines to release the free michellamines. The synthesis of several michellamine analogues, including ent-michellamines, is outlined. Results of anti-HIV assays are presented.

  DOI：

  10.1021/jo9908187
• 作为产物：
  描述：

  5-bromo-1,8-dimethoxy-3-methylnaphthalene 在 正丁基锂 、 硼酸三甲酯 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.5h， 以92%的产率得到(4,5-二甲氧基-7-甲基-1-萘基)硼酸
  参考文献：
  名称：

  防手性联芳基偶合与手性催化剂：合成抗虫药萘基异喹啉碱生物碱丹参碱B和AncistroealaineA。

  摘要：

  [反应：见正文]描述了萘基异喹啉生物碱抗坏血酸A的首次全合成。关键步骤是通过Suzuki偶联构建旋转受阻的立体立体联芳基轴。尽管仅观察到二氢异喹啉部分中立体中心的弱内部不对称诱导作用，但通过使用手性催化剂，可以获得更好的阻转异构体比率，有利于顺反安息香B。两种生物碱，特别是顺坦古藤碱B，都显示出很高的抗霉菌活性。

  DOI：

  10.1021/ol0347693

文献信息

• The ‘lactone method’: enantioselective preparation of novel P,N-biaryl ligands and their use in the synthesis of the biarylic alkaloids, ancistrotanzanine B and ancistroealaine A
  作者：Gerhard Bringmann、Robert-Michael Pfeifer、Petra Schreiber、Kristina Hartner、Michaela Schraut、Matthias Breuning

  DOI：10.1016/j.tet.2003.12.070

  日期：2004.5

  The ‘lactone method’ is a versatile tool for the atroposelective synthesis of axially chiral biaryls. The potential and scope of the concept are highlighted, in particular with respect to its use in the preparation of natural products and chiral auxiliaries. As a new application, the synthesis of novel axially chiral phosphineamines in enantiopure form is described; these ligands were used in the asymmetric

  “内酯法”是用于轴向手性联芳基的对映选择性合成的通用工具。强调了该概念的潜力和范围，特别是在其用于制备天然产物和手性助剂方面。作为一种新的应用，描述了对映体纯形式的新型轴向手性膦胺的合成。这些配体用于二元天然产物ancistrotanzanine B和ancistroealaine A的分子部分的不对称Suzuki交叉偶联。
• Atroposelective Biaryl Coupling with Chiral Catalysts:  Total Synthesis of the Antileishmanial Naphthylisoquinoline Alkaloids Ancistrotanzanine B and Ancistroealaine A
  作者：Gerhard Bringmann、Andreas Hamm、Michaela Schraut

  DOI：10.1021/ol0347693

  日期：2003.8.1

  [reaction: see text] The first total synthesis of the naphthylisoquinoline alkaloid ancistrotanzanine B and its atropo-diastereomer, ancistroealaine A, is described. The key step is the construction of the rotationally hindered and thus stereogenic biaryl axis by Suzuki coupling. While only weak internal asymmetric inductions by the stereogenic center in the dihydroisoquinoline part were observed,

  [反应：见正文]描述了萘基异喹啉生物碱抗坏血酸A的首次全合成。关键步骤是通过Suzuki偶联构建旋转受阻的立体立体联芳基轴。尽管仅观察到二氢异喹啉部分中立体中心的弱内部不对称诱导作用，但通过使用手性催化剂，可以获得更好的阻转异构体比率，有利于顺反安息香B。两种生物碱，特别是顺坦古藤碱B，都显示出很高的抗霉菌活性。
• Total Synthesis of Michellamines A−C, Korupensamines A−D, and Ancistrobrevine B
  作者：Thomas R. Hoye、Minzhang Chen、Bac Hoang、Liang Mi、Owen P. Priest

  DOI：10.1021/jo9908187

  日期：1999.9.1

  Efficient syntheses of the title compounds have been developed. Several strategies for preparation of each of the naphthalene and tetrahydroisoquinoline (THIQ) portions were developed. Initial attempts to use benzyne plus furan cycloaddition reactions were thwarted by the unfavorable sense of the regiochemical outcome. An interesting annulation reaction of benzynes derived from 2,4-dibromophenol derivatives formed the core of the shortest naphthalene synthesis. An alternative annulation initiated by the addition of a benzylic sulfone anion to methyl crotonate led to an efficient naphthol synthesis amenable to large scale. The THIQ synthesis of Bringmann was used initially and subsequently complemented by a route whose key step involved the opening of N-tosyl-2-methylethyleneimine by a 3,5-dimethoxyphenylcuprate reagent. The results from a variety of aryl cross-coupling reactions are described. Suzuki coupling of the boronic acid derived from the naphthalene moiety with a THIQ-iodide was the most generally effective method for forming the hindered biaryl bond. The korupensamines and ancistrobrevine B were then revealed by deprotection. The oxidative coupling of several 4-aryl-1-naphthols to indigoids (cross ring naphthoquinones) with silver oxide effected the critical dimerization reaction needed to establish the michellamine skeleton. For the perbenzylated precursor, hydrogen over palladium on carbon both reductively bleached the indigoid and hydrogenolyzed the benzyl ethers and amines to release the free michellamines. The synthesis of several michellamine analogues, including ent-michellamines, is outlined. Results of anti-HIV assays are presented.
• Unprecedented Direct Asymmetric Total Syntheses of 5,8’‐Naphthylisoquinoline Alkaloids from their Fully Substituted Precursors Employing a Novel Nickel/N,N‐ligand‐Catalyzed Atroposelective Cross‐Coupling Reaction
  作者：Dino Berthold、Willem A. L. van Otterlo

  DOI：10.1002/chem.202302070

  日期：2023.11.2

  Four different 5,8’-coupled naphthylisoquinoline alkaloids have been prepared via a general and concise synthetic pathway directly from the corresponding cross-coupling reaction precursors. For the cross-coupling key step, a new Negishi cross-coupling reaction, employing a Ni/N,N-ligand-based catalyst providing the natural products in good yields and high enantiomeric purities, has been developed.

  四种不同的 5,8'-偶联萘基异喹啉生物碱已通过通用且简洁的合成途径直接从相应的交叉偶联反应前体制备。对于交叉偶联的关键步骤，开发了一种新的根岸交叉偶联反应，采用基于 Ni/N,N-配体的催化剂，以良好的收率和高对映体纯度提供天然产物。此外，我们还报告了一种在萘基异喹啉天然产物中发现的北部 1,8-二氧基萘结构单元的新方法，利用 Hartwig 的硼化/甲基化策略，可以有效安装正交保护基团。