3-氟-5,6,7,8-四氢-2-萘酚 | 709032-00-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 中文名称: 3-氟-5,6,7,8-四氢-2-萘酚
• 中文别名: 7-[[1-(3-溴苯基)环戊羰基]氨基]-3-甲基-8-羰基-5-硫杂-1-氮杂二环[4.2.0]辛-2-烯-2-羧酸钠
• 英文名称: 3-fluoro-5,6,7,8-tetrahydronaphthalen-2-ol
• CAS: 709032-00-8
• 化学式: C₁₀H₁₁FO
• 分子量: 166.195
• InChiKey: KNRQRBNALPBOOD-UHFFFAOYSA-N

物化性质

• 沸点：
  263.2±40.0 °C(Predicted)
• 密度：
  1.196±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  4,4a,5,6,7,8-六氢-3H-萘-2-酮 在 正丁基锂 、 水 、 Selectfluor 、 三乙胺 、 二异丙胺 、 甲烷磺酰基叠氮化物 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 反应 19.16h， 生成 3-氟-5,6,7,8-四氢-2-萘酚
  参考文献：
  名称：

  Preparation of o-Fluorophenols from Nonaromatic Precursors: Mechanistic Considerations for Adaptation to Fluorine-18 Radiolabeling

  摘要：

  The preparation of fluorine-18 labeled o-fluorophenols at high specific activity is challenging and requires use of [F-18]fluoride ion as the radioisotope source. As a novel, alternative approach, we found that treatment of alpha-diazocyclohexenones with Selectfluor and Et3N center dot 3HF followed by HF elimination and tautomerization afforded o-fluorophenols regioselectively and rapidly. To adapt this chemistry to F-18 radiolabeling, using bromine electrophiles in place of Selectfluor gave the o-fluorophenol via an alpha-bromo-alpha-fluoroketone intermediate in lower but still reasonable yields.

  DOI：

  10.1021/acs.orglett.5b02640

文献信息

• Chiral Anion Phase-Transfer Catalysis Applied to the Direct Enantioselective Fluorinative Dearomatization of Phenols
  作者：Robert J. Phipps、F. Dean Toste

  DOI：10.1021/ja311798q

  日期：2013.1.30

  ambient reaction conditions with high enantioselectivity. The close relationship of the products with well-studied o-quinols provides numerous avenues for synthetic elaboration and exciting opportunities for bioisosteric replacement of hydroxyl with fluorine in natural products.

  手性阴离子相转移催化使由 BINOL 衍生的磷酸盐催化的苯酚直接和高度对映选择性氟化脱芳构化成为可能。该过程在环境反应条件下以高对映选择性有效地将简单、容易获得的酚类转化为带有反应性官能团的氟化手性小分子。产品与经过充分研究的邻羟基喹啉的密切关系为合成加工提供了许多途径，并为天然产物中的氟生物等排置换羟基提供了令人兴奋的机会。
• [EN] ASYMMETRIC ELECTROPHILIC FLUORINATION USING AN ANIONIC CHIRAL PHASE-TRANSFER CATALYST<br/>[FR] FLUORATION ÉLECTROPHILE ASYMÉTRIQUE UTILISANT UN CATALYSEUR DE TRANSFERT DE PHASE CHIRAL ANIONIQUE
  申请人：UNIV CALIFORNIA

  公开号：WO2013096971A1

  公开（公告）日：2013-06-27

  The discovery of distinct modes of asymmetric catalysis has the potential to rapidly advance chemists' ability to build enantioenriched molecules. As an example, the use of chiral cation salts as phase-transfer catalysts for anionic reagents has enabled a vast set of enantioselective transformations. A largely overlooked analogous mechanism wherein a chiral anionic catalyst brings a cationic species into solution is itself a powerful method. The concept is broadly applicable to a number of different reaction pathways, including to the enantioselective fluorocyclization of olefins, and dearomatization of aromatic systems with a cationic electrophile-transferring (e.g., fluorinating) agent and a chiral phosphate catalyst. The reactions proceed in high yield and stereoselectivity. The compounds and methods of the invention are of particular value, especially considering the scarcity of alternative approaches.

  发现不对称催化的不同模式具有潜力快速推动化学家构建手性富集分子的能力。例如，使用手性阳离子盐作为相转移催化剂用于阴离子试剂已经实现了大量手性选择性转化。一个被大多数人忽视的类似机制是手性阴离子催化剂将阳离子物种溶解到溶液中，这本身就是一种强大的方法。这一概念广泛适用于许多不同的反应途径，包括对烯烃进行手性选择性氟环化和用阳离子亲电试剂转移（例如，氟化）剂和手性磷酸盐催化剂进行芳香系统去芳构化。这些反应产率高，立体选择性好。该发明的化合物和方法具有特殊价值，尤其考虑到替代方法的稀缺性。
• ASYMMETRIC ELECTROPHILIC FLUORINATION USING AN ANIONIC CHIRAL PHASE-TRANSFER CATALYST
  申请人：THE REGENTS OF THE UNIVERSITY OF CALIFORNIA

  公开号：US20140350253A1

  公开（公告）日：2014-11-27

  The discovery of distinct modes of asymmetric catalysis has the potential to rapidly advance chemists' ability to build enantioenriched molecules. As an example, the use of chiral cation salts as phase-transfer catalysts for anionic reagents has enabled a vast set of enantioselective transformations. A largely overlooked analogous mechanism wherein a chiral anionic catalyst brings a cationic species into solution is itself a powerful method. The concept is broadly applicable to a number of different reaction pathways, including to the enantioselective fluorocyclization of olefins, and dearomatization of aromatic systems with a cationic electrophile-transferring (e.g., fluorinating) agent and a chiral phosphate catalyst. The reactions proceed in high yield and stereoselectivity. The compounds and methods of the invention are of particular value, especially considering the scarcity of alternative approaches.

  不对称催化的不同模式的发现有潜力快速推进化学家构建对映富集分子的能力。例如，手性阳离子盐作为相转移催化剂用于阴离子试剂的使用已经实现了广泛的对映选择性转化。一个被大多数人忽视的类似机理是手性阴离子催化剂将阳离子物种溶解进溶液中的强大方法。这个概念广泛适用于许多不同的反应途径，包括烯烃的对映选择性氟杂环化和芳香体系的脱芳香化，使用离子型电子亲合试剂（例如氟化试剂）和手性磷酸盐催化剂。反应具有高产率和立体选择性。该发明的化合物和方法具有特殊价值，特别是考虑到替代方法的稀缺性。
• US9981977B2
  申请人：——

  公开号：US9981977B2

  公开（公告）日：2018-05-29
• Preparation of <i>o</i>-Fluorophenols from Nonaromatic Precursors: Mechanistic Considerations for Adaptation to Fluorine-18 Radiolabeling
  作者：Norio Yasui、Christopher G. Mayne、John A. Katzenellenbogen

  DOI：10.1021/acs.orglett.5b02640

  日期：2015.11.20

  The preparation of fluorine-18 labeled o-fluorophenols at high specific activity is challenging and requires use of [F-18]fluoride ion as the radioisotope source. As a novel, alternative approach, we found that treatment of alpha-diazocyclohexenones with Selectfluor and Et3N center dot 3HF followed by HF elimination and tautomerization afforded o-fluorophenols regioselectively and rapidly. To adapt this chemistry to F-18 radiolabeling, using bromine electrophiles in place of Selectfluor gave the o-fluorophenol via an alpha-bromo-alpha-fluoroketone intermediate in lower but still reasonable yields.