1-(2-furyl)cyclohexan-1-ol | 36169-67-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(2-furyl)cyclohexan-1-ol
• 英文别名: 1-(furan-2-yl)cyclohexanol；1-(furan-2-yl)cyclohexan-1-ol；2-(1-Hydroxycyclohexyl)-furan
• CAS: 36169-67-2
• 化学式: C₁₀H₁₄O₂
• 分子量: 166.22
• InChiKey: CEKOLRUYQTZZBJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  33.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(2-furyl)cyclohexan-1-ol 在 rose bengal 水 、 氧气 作用下， 以 丙酮 为溶剂， 反应 7.0h， 以60%的产率得到5-羟基呋喃-2(5H)-酮
  参考文献：
  名称：

  Singlet oxygen oxidation of substituted furans to 5-hydroxy-2(5H)-furanone

  摘要：

  The conditions for the regiospecific singlet oxygen oxidation of various 2,4-disubstituted furans 9 to 4-substituted-2 (5H)-furanones 3 are developed. The presence of a C-2 substituent (e.g., trimethylsilyl, tert-butyldimethylsilyl, or tributylstannyl) in 9 is an absolute requirement for the formation of the 4-substituted-5-hydroxy-2(5H)-furanone regioisomer 3. When the C-2 substituent is triethylsilyl (TES) or TBDMS, however, apart from 3, the corresponding 5-trialkylsiloxy derivative 11 is also isolated in a significant amount. These silyl acetals are unexpectedly stable but can be hydrolyzed back to 3 on stirring with dilute acid. The formation of silyl acetals, to our knowledge, has never been reported in the singlet oxygen oxidation of (trialkylsilyl)furan. A plausible mechanism for their formation is proposed. The presence of a catalytic amount of water in the oxidation of 2-(trialkylsilyl)-4-substituted-furans not only eliminates the formation of the silyl acetals but also speeds up the rate of the oxidation process. Moreover, the oxidation can then be carried out at 0-degrees-C instead of at -78-degrees-C. Oxidation of 2-(1-hydroxyalkyl)-4-substituted-furans in the absence of a reducing agent gives little or no sign of 2,5-disubstituted-6-hydroxy-3(2H)-pyranone 23 but instead 26 selectively. Thus, the (1-hydroxy)alkyl group can be utilized as the trialkylsilyl or trialkylstannyl group in dictating the regioselectivity in the singlet oxygen oxidation of substituted furans.

  DOI：

  10.1021/jo00025a012
• 作为产物：
  描述：

  呋喃 、 环己酮 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 以830 mg的产率得到1-(2-furyl)cyclohexan-1-ol
  参考文献：
  名称：

  对映体生物催化氧化还原异构化。

  摘要：

  醇脱氢酶可以作为强大的催化剂，通过容易获得的 Achmatowicz 型吡喃酮的对映体动态氧化还原异构化来制备光学纯的 γ-羟基-δ-内酯。这种化学启发和纯生物催化的解释模仿传统的金属介导的“借氢”方法，在分子结构和相互转换的官能团之间重组氢化物，有效地扩展了酶工具箱，并为多酶级联和定制细胞工厂的组装提供了新的机会。

  DOI：

  10.1002/anie.201804911

文献信息

• Manganese-Catalyzed Achmatowicz Rearrangement Using Green Oxidant H₂O₂
  作者：Qingzhao Xing、Zhe Hao、Jing Hou、Gaoqiang Li、Ziwei Gao、Jing Gou、Chaoqun Li、Binxun Yu

  DOI：10.1021/acs.joc.1c00858

  日期：2021.7.16

  catalytic methods for the oxidative furan-recyclizations remain scarcely investigated. Given this, we report a means of manganese-catalyzed oxidations of furan with low loading, achieving the Achmatowicz rearrangement in the presence of hydrogen peroxide as an environmentally benign oxidant under mild conditions with wide functional group compatibility.

  在生物质衍生的呋喃转化的背景下，氧化反应得到了广泛的研究。然而，与利用化学计量氧化剂（如m- CPBA 和 NBS）的大量文献相比，氧化呋喃循环的催化方法仍然很少被研究。鉴于此，我们报告了一种低负载量的锰催化氧化呋喃的方法，在具有广泛官能团兼容性的温和条件下，在作为环境友好氧化剂的过氧化氢存在下实现 Achmatowicz 重排。
• Catalytic Enantioselective Aza-Piancatelli Rearrangement
  作者：Nitin Patil、Amol Gade

  DOI：10.1055/s-0036-1558952

  日期：——

  The design and development of an enantioselective aza-­Piancatelli rearrangement reaction are described. In the presence of a chiral phosphoric acid catalyst, furylcarbinols react with anilines to ­afford highly functionalized cyclopentenones with excellent diastereo- and enantioselectivities. The process was shown to be scalable, and up to 1 gram of starting material could be employed under mild reaction

  描述了对映选择性 aza-Piancatelli 重排反应的设计和开发。在手性磷酸催化剂的存在下，呋喃基甲醇与苯胺反应以提供具有优异非对映选择性和对映选择性的高度官能化的环戊烯酮。该过程被证明是可扩展的，在温和的反应条件下可以使用多达 1 克的起始材料。
• CtD strategy to construct stereochemically complex and structurally diverse compounds from griseofulvin
  作者：Li Zhu、Rui-Han Zhao、Yu Li、Gong-Qing Liu、Yu Zhao

  DOI：10.1039/d1cc04007c

  日期：——

  stereochemically complex and structurally diverse small molecules from natural products using ring-distortion reactions, was applied in the synthesis of a 47-member compound collection from the natural product griseofulvin. A Tsuji–Trost allylation and oxa-Michael cyclization tandem reaction was used for the first time in the CtD strategy to generate complex ring fused compounds.

  多样性的复杂性 (CtD) 策略是一种使用环变形反应从天然产物合成立体化学复杂和结构多样的小分子的策略，用于从天然产物灰黄霉素合成 47 个成员的化合物集合。在 CtD 策略中首次使用 Tsuji-Trost 烯丙基化和 oxa-Michael 环化串联反应来生成复杂的稠环化合物。
• The binary reagent PhI(OAc)2-Mg(CIO4)2:a SET induced ring enlargement of furan derivatives into pyranones
  作者：Antonella De Mico、Roberto Margarita、Giovanni Piancatelli

  DOI：10.1016/0040-4039(95)91393-k

  日期：1995.5

  The binary reagent PhI(OAc)2-Mg(CIO4)2 is very efficient for a high conversion of (2-furyl)-1-alcohols into pyranones. The reaction mechanism can be explained in terms of a SET process, with the generation of a cation radical as key intermediate.

  二元试剂PhI（OAc）2 -Mg（CIO 4）2对于将（2-呋喃基）-1-醇高度转化为吡喃酮非常有效。反应机理可以用SET过程来解释，其中阳离子自由基的产生是关键的中间体。
• Unprecedented Reactivity of γ‐Amino Cyclopentenone Enables Diversity‐Oriented Access to Functionalized Indoles and Indole‐Annulated Ring Structures
  作者：Chenna Jagadeesh、Biplab Mondal、Sourav Pramanik、Dinabandhu Das、Jaideep Saha

  DOI：10.1002/anie.202016015

  日期：2021.4.12

  indole derivatives, which is developed in the current study. Herein, a vast range of C3/N‐indolyl enones and indole alkaloid‐like compound were accessed in excellent yields (up to 99 %) and selectivity through a one‐pot operation. The mechanism most likely involves an unprecedented trait of Piancatelli‐type rearrangement where influence of the gem‐diaryl group appeared crucial.

  观察到意外的路易斯酸促进了环戊烯酮上潜在的反应性γ-氨基的置换，这为烯酮官能化和吲哚衍生物的环化提供了无与伦比的机会，这是本研究开发的。在此，通过一锅操作获得了种类繁多的C3 / N-吲哚基烯酮和吲哚类生物碱化合物，收率极高（高达99％）和选择性。该机制最有可能涉及Piancatelli型重排的前所未有的特征，其中，宝石-二芳基的影响显得至关重要。