(1S)-1-(1'-adamantyl)-2-bromo-1-hydroxyethane | 130187-87-0

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代醇
• 英文名称: (1S)-1-(1'-adamantyl)-2-bromo-1-hydroxyethane
• 英文别名: (S)-1-(adamantan-1-yl)-2-bromoethanol；(S)-1-(Adamantan-1-yl)-2-bromoethan-1-ol；(1S)-1-(1-adamantyl)-2-bromoethanol
• CAS: 130187-87-0；145238-44-4
• 化学式: C₁₂H₁₉BrO
• 分子量: 259.186
• InChiKey: JOPAFDSOJPEXPK-LTMLNTECSA-N

物化性质

• 沸点：
  330.9±15.0 °C(Predicted)
• 密度：
  1.435±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1S)-1-(1'-adamantyl)-2-bromo-1-hydroxyethane 在 sodium hydroxide 、 正丁基锂 、 三氟甲磺酸三甲基硅酯 、 三氟化硼乙醚 作用下， 以 乙醚 、 乙腈 为溶剂， 生成 (1S,3R)-3-(1'-adamantyl)-5,6-(cyclohexylidenedioxy)-3,4-dihydro-1-<(N-formylamino)methyl>-1H-2-benzopyran
  参考文献：
  名称：

  The enantioselective synthesis of the potent dopamine D1 agonist (1R,3S)-3-(1'-adamantyl)-1-(aminomethyl)-3,4-dihydro-5,6-dihydroxy-1H-2-benzopyran (A77636)

  摘要：

  The synthesis of both enantiomers of the title compound is described. The corresponding racemic compound (+/-)-1 was previously shown to be a highly potent and selective dopamine Dl agonist. Key to the synthesis of the enantiomers was the oxazaborolidine-catalyzed asymmetric reduction of the alpha-bromomethyl ketone 12 which led to the optically enriched epoxide 7. An aryllithium addition to the epoxide followed by a diastereospecific cyclization to the isochroman system furnished compound 17, which was deprotected to afford (-)-1 with >99.5% optical purity.

  DOI：

  10.1021/jo00052a025
• 作为产物：
  描述：

  1-金刚烷基溴甲酮 在 (S)-3,3-diphenyltetrahydro-3H-1l4-spiro[pyrrolo[1,2-c][1,3,2]oxazaborole-1,2'-[1,3,2]dioxaborolane] 、 dimethyl sulfide borane 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 (1S)-1-(1'-adamantyl)-2-bromo-1-hydroxyethane
  参考文献：
  名称：

  螺硼酸酯催化硼烷还原 2-卤代酮制备手性环氧化物：在光学纯 1,2-羟基醚和 1,2-叠氮醇合成中的应用

  摘要：

  描述了以 10% 螺氨基硼酸酯1作为催化剂，对映选择性硼烷介导的多种 2-卤代酮的还原反应。通过 2-卤代醇的简单基础处理，可以高产率和优异的对映体纯度（高达 99% ee）获得光学活性环氧化物。在不同的反应条件下研究了环氧乙烷与酚盐或叠氮化钠的开环，得到具有优异对映选择性 (99% ee) 和良好至高化学收率的非外消旋 1,2-羟基醚和 1,2-叠氮醇。

  DOI：

  10.1021/jo102294j

文献信息

• Synthesis of enantiopure 1,2-azido and 1,2-amino alcohols via regio- and stereoselective ring-opening of enantiopure epoxides by sodium azide in hot water
  作者：Hai-Yang Wang、Kun Huang、Melvin De Jesús、Sandraliz Espinosa、Luis E. Piñero-Santiago、Charles L. Barnes、Margarita Ortiz-Marciales

  DOI：10.1016/j.tetasy.2015.12.002

  日期：2016.2

  A practical and convenient method for the efficient and regio- and stereoselective ring-opening of enantiopure monosubstituted epoxides by sodium azide under hydrolytic conditions is reported. The ring-opening of enantiopure styryl and pyridyl (S)-epoxides by N3 - in hot water takes place preferentially at the internal position with complete inversion of configuration to produce (R)-2-azido ethanols

  报道了一种实用且方便的方法，用于在水解条件下通过叠氮化钠对映体纯单取代环氧化物进行有效的区域和立体选择性开环。对映体纯苯乙烯基和吡啶基 (S)-环氧化物在热水中通过 N3 - 开环优先在内部位置发生，构型完全反转，生成对映体含量高达 99% 的 (R)-2-叠氮基乙醇区域选择性，而(S)-金刚烷基环氧乙烷主要以优异的收率提供(S)-1-金刚烷基-2-叠氮基乙醇。一般来说，通过在水/THF中用PPh3还原手性1,2-叠氮基乙醇，可以高收率和优异对映体纯度获得1,2-氨基乙醇，然后转化为Boc或乙酰胺衍生物。
• Chiral Epoxides via Borane Reduction of 2-Haloketones Catalyzed by Spiroborate Ester: Application to the Synthesis of Optically Pure 1,2-Hydroxy Ethers and 1,2-Azido Alcohols
  作者：Kun Huang、Haiyang Wang、Viatcheslav Stepanenko、Melvin De Jesús、Carilyn Torruellas、Wildeliz Correa、Margarita Ortiz-Marciales

  DOI：10.1021/jo102294j

  日期：2011.3.18

  with 10% spiroaminoborate ester 1 as catalyst is described. By a simple basic workup of 2-halohydrins, optically active epoxides are obtained in high yield and with excellent enantiopurity (up to 99% ee). Ring-opening of oxiranes with phenoxides or sodium azide is investigated under different reaction conditions affording nonracemic 1,2-hydroxy ethers and 1,2-azido alcohols with excellent enantioselectivity

  描述了以 10% 螺氨基硼酸酯1作为催化剂，对映选择性硼烷介导的多种 2-卤代酮的还原反应。通过 2-卤代醇的简单基础处理，可以高产率和优异的对映体纯度（高达 99% ee）获得光学活性环氧化物。在不同的反应条件下研究了环氧乙烷与酚盐或叠氮化钠的开环，得到具有优异对映选择性 (99% ee) 和良好至高化学收率的非外消旋 1,2-羟基醚和 1,2-叠氮醇。
• The enantioselective synthesis of the potent dopamine D1 agonist (1R,3S)-3-(1'-adamantyl)-1-(aminomethyl)-3,4-dihydro-5,6-dihydroxy-1H-2-benzopyran (A77636)
  作者：Michael P. DeNinno、Richard J. Perner、Howard E. Morton、Stanley DiDomenico

  DOI：10.1021/jo00052a025

  日期：1992.12

  The synthesis of both enantiomers of the title compound is described. The corresponding racemic compound (+/-)-1 was previously shown to be a highly potent and selective dopamine Dl agonist. Key to the synthesis of the enantiomers was the oxazaborolidine-catalyzed asymmetric reduction of the alpha-bromomethyl ketone 12 which led to the optically enriched epoxide 7. An aryllithium addition to the epoxide followed by a diastereospecific cyclization to the isochroman system furnished compound 17, which was deprotected to afford (-)-1 with >99.5% optical purity.