2,3-dihydro-1H-inden-2-d-2-ol | 56588-28-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: 2,3-dihydro-1H-inden-2-d-2-ol
• 英文别名: 2-Deuterio-1,3-dihydroinden-2-ol
• CAS: 56588-28-4
• 化学式: C₉H₁₀O
• 分子量: 135.17
• InChiKey: KMGCKSAIIHOKCX-QOWOAITPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  2,3-dihydro-1H-inden-2-d-2-ol 在 N-溴代丁二酰亚胺(NBS) 、 sodium azide 、 sodium methylate 、 三溴化磷 、 sodium hydride 作用下， 以 甲醇 、 四氯化碳 、 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 81.75h， 生成 cis-2-azido-1-bromo-2-d-indane
  参考文献：
  名称：

  Enantioselective Synthesis of cis- and trans-2(S)-Amino-1-d-indane:  Debrominative [1,2]-Hydride Shift Rearrangement by Reduction of cis-2-Azido-1-bromoindane with LiAlD₄

  摘要：

  This article describes the synthesis of the racemic and optically pure forms of (1R,2S)-cis- and (1S,2S)-trans-2-Amino-1-d-indanes 2 {94% ee} and 3 {83% ee} (ee determined by H-2 NMR in chiral liquid crystal PBLG/CH2Cl2, Courtieu, J. et al. J. Am. Chem. Soc. 1995, 117, 6520) prepared by LiAlD4 reduction of (+/-)- and (1S,2S)-trans-2-azido-1-bromomoindane (11) {87% ee} and (+/-) and (1R,2S)-cis-2-azido-1-[(methanesulfonyl)oxy]indane (10) {83% ee}, respectively. Whereas the LiAlD4 reduction of trans-2-azido-1-bromomoindane (11) led to cis-2-amino-1-d-indane 2 by a S(N)2 pathway, exclusively, the reduction of cis-1-bromo derivative 12 gave only small amounts of the S(N)2 product trans-2-amino-1-d-indane (3) (15%) accompanied by 2-amino-2-d-indane (4) (85%) in which the deuterium atom is incorporated in alpha position to the amino group. It was established that the primary amine 4 comes from a stereospecific [1,2]-hydride shift rearrangement, We propose that the azido group is reduced first, and the [1,2]-hydride shift rearrangement prevails over the competitive S(N)2 substitution. The exclusive formation of trans-2-amino-1-d-indane (3) requires cis-2-azido-1-[(methanesulfonyl)oxy]indane (10) where the mesylate assisted by electrophilic Li+ cation switches the deuteride attack to the ester carbon and the direct S(N)2 substitution occurs before the azide is reduced.

  DOI：

  10.1021/jo970378o
• 作为产物：
  描述：

  2-茚酮 在 samarium diiodide 、 重水 作用下， 以 四氢呋喃 为溶剂， 反应 0.25h， 以73%的产率得到2,3-dihydro-1H-inden-2-d-2-ol
  参考文献：
  名称：

  以 D2O 为氘源的羰基化合物单电子 Umpolung 还原氘化合成 α-氘醇

  摘要：

  掺入氘可以有效地稳定受体内快速消旋化阻碍的药物和农用化学品候选物的手性中心。在这项工作中，通过使用良性 D2O 作为氘源和温和 SmI2 作为电子供体的单电子 umpolung 还原-氘化方案实现了具有合成挑战性的醇手性中心氘化。该方法的广泛范围和优异的官能团耐受性已通过以高产率合成 43 种各自的 α-氘醇和≥98% 的氘掺入量来展示。这种通用方法的潜在应用已在 6 种氘化药物衍生物、1 种氘化人类激素和 3 种氘化天然产物的合成中得到了例证。

  DOI：

  10.1055/a-1523-3336

文献信息

• 一种α-一氘代醇类化合物、氘代药物的合成方法
  申请人：中国农业大学

  公开号：CN112939732A

  公开（公告）日：2021-06-11

  本发明提供了一种α‑一氘代醇类化合物及用于制备α‑一氘代醇类化合物的一种醛酮类化合物的还原氘化方法，通式(1)所示的醛酮类化合物与二价镧系过渡金属化合物、氘供体试剂在有机溶剂I中反应生成通式(2)所示的α‑一氘代醇类化合物。本发明建立了一种基于单电子转移还原氘化反应的醛酮类化合物的还原氘化方法用于制备通式(2)所示的α‑一氘代醇类化合物，及其醛酮类药物、激素、天然产物的氘代衍生物。本方法具有产物氘代率高、区位选择性好、化学选择性好、试剂价格低廉、操作简单、条件温和、底物适用范围广的优点。相比现有的H/D交换方法，本发明氘供体试剂用量小，可以显著降低成本，并提高氘原子的利用率。
• A mass spectral investigation of water and acetic acid elimination from 1- and 2-indan derivatives
  作者：G. S. Groenewold、M. L. Gross、R. Zey

  DOI：10.1002/oms.1210170905

  日期：1982.9

  AbstractWater and acetic acid eliminations from 1‐ and 2‐indan derivatives have been investigated. Deuterium labeling, high resolution peak matching and the metastable peak analysis capabilities of a high resolution triple analyzer (E B E) mass spectrometer were employed to examine the eliminations. These experiments showed that water was lost from 1‐indanol via 1,2 and 1,3 processes. These results contrast with those obtained for 1‐tetralol, which specifically eliminates water in a 1,4 process involving the benzylic hydrogens. Water elimination from 2‐indanol is preceded by a slow hydroxyl‐benzylic hydrogen exchange and proceeds specifically 1,2. Water losses from both 1‐ and 2‐indanol are characterized by large kinetic energy releases. Acetic acid elimination is shown to occur specifically 1,3 from 1‐acetoxyindan and 1,2 from 2‐acetoxyindan.
• Synthesis of α-Deuterioalcohols by Single-Electron Umpolung Reductive Deuteration of Carbonyls Using D2O as Deuterium Source
  作者：Yuxia Hou、Zemin Lai、Lei Ning、Yixuan Li、Jie An、Hengzhao Li、Ailing Li

  DOI：10.1055/a-1523-3336

  日期：2021.7

  Deuterium incorporation can effectively stabilize the chiral centers of drug and agrochemical candidates that hampered by rapid in vivo racemization. In this work, the synthetically challenging chiral-center deuteration of alcohols has been achieved via a single-electron umpolung reductive-deuteration protocol using benign D2O as deuterium source and mild SmI2 as electron donor. The broad scope and

  掺入氘可以有效地稳定受体内快速消旋化阻碍的药物和农用化学品候选物的手性中心。在这项工作中，通过使用良性 D2O 作为氘源和温和 SmI2 作为电子供体的单电子 umpolung 还原-氘化方案实现了具有合成挑战性的醇手性中心氘化。该方法的广泛范围和优异的官能团耐受性已通过以高产率合成 43 种各自的 α-氘醇和≥98% 的氘掺入量来展示。这种通用方法的潜在应用已在 6 种氘化药物衍生物、1 种氘化人类激素和 3 种氘化天然产物的合成中得到了例证。
• Enantioselective Synthesis of <i>cis</i>- and <i>trans</i>-2(<i>S</i>)-Amino-1-<i>d</i>-indane:  Debrominative [1,2]-Hydride Shift Rearrangement by Reduction of <i>cis</i>-2-Azido-1-bromoindane with LiAlD₄
  作者：Anton A. Mitrochkine、Ingrid Blain、Christelle Bit、Cécile Canlet、Sébastien Pierre、Jacques Courtieu、Marius Réglier

  DOI：10.1021/jo970378o

  日期：1997.9.1

  This article describes the synthesis of the racemic and optically pure forms of (1R,2S)-cis- and (1S,2S)-trans-2-Amino-1-d-indanes 2 94% ee} and 3 83% ee} (ee determined by H-2 NMR in chiral liquid crystal PBLG/CH2Cl2, Courtieu, J. et al. J. Am. Chem. Soc. 1995, 117, 6520) prepared by LiAlD4 reduction of (+/-)- and (1S,2S)-trans-2-azido-1-bromomoindane (11) 87% ee} and (+/-) and (1R,2S)-cis-2-azido-1-[(methanesulfonyl)oxy]indane (10) 83% ee}, respectively. Whereas the LiAlD4 reduction of trans-2-azido-1-bromomoindane (11) led to cis-2-amino-1-d-indane 2 by a S(N)2 pathway, exclusively, the reduction of cis-1-bromo derivative 12 gave only small amounts of the S(N)2 product trans-2-amino-1-d-indane (3) (15%) accompanied by 2-amino-2-d-indane (4) (85%) in which the deuterium atom is incorporated in alpha position to the amino group. It was established that the primary amine 4 comes from a stereospecific [1,2]-hydride shift rearrangement, We propose that the azido group is reduced first, and the [1,2]-hydride shift rearrangement prevails over the competitive S(N)2 substitution. The exclusive formation of trans-2-amino-1-d-indane (3) requires cis-2-azido-1-[(methanesulfonyl)oxy]indane (10) where the mesylate assisted by electrophilic Li+ cation switches the deuteride attack to the ester carbon and the direct S(N)2 substitution occurs before the azide is reduced.