(4-methylfuran-3-yl)methanol | 117657-94-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: (4-methylfuran-3-yl)methanol
• CAS: 117657-94-0
• 化学式: C₆H₈O₂
• 分子量: 112.128
• InChiKey: CBTWDJVVWKFKBU-UHFFFAOYSA-N

物化性质

• 沸点：
  91-93 °C(Press: 20 Torr)
• 密度：
  1.095±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  (4-methylfuran-3-yl)methanol 在 manganese(IV) oxide 、 lithium hydroxide 、 4 A molecular sieve 、 pH 7 aq. phosphate buffer 、 Raney nickel (W-4) 、 三氟甲磺酸二丁硼 、 双氧水 、 氧气 、 rose bengal 、 氟化氢吡啶 、 三乙胺 、 N,N-二异丙基乙胺 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 32.58h， 生成 trimethyl (Z,3R)-3-hydroxy-1-methylbut-1-ene-1,2,4-tricarboxylate
  参考文献：
  名称：

  Synthetic studies on tautomycin

  摘要：

  The 2,3-disubstituted maleic anhydride segment of tautomycin has been synthesized in optically active form. Oxidation of 3,4-disubsrituted furan employing singlet oxygen completes the construction of the maleic anhydride moiety. Esterification of the maleic anhydride segment without protecting anhydride moiety resulted in the successful coupling reaction with fragment derived from tautomycin.

  DOI：

  10.1016/s0040-4020(01)85365-5
• 作为产物：
  描述：

  2-(1-nitropropan-2-yl)-1,3-dioxolane 在 三乙烯二胺 、 盐酸 、 水 、 barium(II) hydroxide 作用下， 以 乙二醇二甲醚 、 丙酮 为溶剂， 反应 53.0h， 生成 (4-methylfuran-3-yl)methanol
  参考文献：
  名称：

  An Enantioselective Approach to Furanoeremophilanes: (+)-9-Oxoeuryopsin

  摘要：

  An enantioselective total synthesis of the furanoeremophilane sesquiterpene (+)-9-oxoeuryopsin 1 is reported. The synthesis involves as a key step a copper(II) triflate catalyzed tandem asymmetric conjugate addition of AlMe3 to 2-methyl-2-cyclohexen-1-one with the Feringa (S,R,R)-phosphoramidite binaphthol ligand, followed by aldol condensation of the resulting aluminum enolate with 4-methyl-3-furaldehyde 4. This tandem transformation has not been previously reported with a 2-substituted-2-cyclohexen-1-one. Conventional functional group manipulations completed the synthesis.

  DOI：

  10.1021/jo400399q

文献信息

• The Influence of Substitution on Thiol-Induced Oxanorbornadiene Fragmentation
  作者：Lucrezia De Pascalis、Mei-Kwan Yau、Dennis Svatunek、Zhuoting Tan、Srinivas Tekkam、K. N. Houk、M. G. Finn

  DOI：10.1021/acs.orglett.1c01164

  日期：2021.5.7

  Oxanorbornadienes (ONDs) undergo facile Michael addition with thiols and then fragment by a retro-Diels–Alder (rDA) reaction, a unique two-step sequence among electrophilic cleavable linkages. The rDA reaction rate was explored as a function of the furan structure, with substituents at the 2- and 5-positions found to be the most influential and the fragmentation rate to be inversely correlated with

  氧杂降冰片二烯 (OND) 与硫醇进行简单的迈克尔加成，然后通过逆狄尔斯-阿尔德 (rDA) 反应进行片段化，这是亲电可切割键之间的独特两步序列。研究了 rDA 反应速率与呋喃结构的函数关系，发现 2 位和 5 位的取代基影响最大，碎裂率与吸电子能力呈负相关。密度泛函理论计算提供了与实验测量的 OND rDA 率的极好相关性。
• A Direct Synthesis of Highly Substituted π‐Rich Aromatic Heterocycles from Oxetanes
  作者：Alexander R. White、Ryan A. Kozlowski、Shiou‐Chuan Tsai、Christopher D. Vanderwal

  DOI：10.1002/anie.201704119

  日期：2017.8.21

  five-membered heterocycles has driven the development of new methods for their synthesis for more than a century. Here, we disclose a general and reliable reaction manifold for the construction of highly substituted heterocycles through a facile Lewis-acid-catalyzed oxetane rearrangement. Notably, this methodology employs a keto-oxetane motif as a 1,4-dicarbonyl surrogate, which can be synthesized using

  超过一个世纪以来，普遍使用富含π的五元杂环。在这里，我们公开了一种通过可靠的路易斯酸催化的氧杂环丁烷重排构建高度取代的杂环的通用而可靠的反应流形。值得注意的是，该方法采用酮-氧杂环丁烷基序作为1,4-二羰基替代物，可以使用稳固的烷基化或烯基化反应合成，因此无需通过缩聚原料接触1,4-二羰基化合物。我们利用这种反应性来生成各种取代的呋喃和吡咯，并扩展了这种方法以生产其苯并稠合的形式。
• The regiospecific formation and reactions of 4-lithio-2-(t-butyldimethylsilyl)- 3-(hydroxymethyl)furan: An approach to 3,4-disubstituted furans.
  作者：Edward J. Bures、Brian A. Keay

  DOI：10.1016/s0040-4039(00)80267-1

  日期：1988.1

  4-Lithio-2-(t-butyldimethylsilyl)-3-(hydroxymethyl)furan, generated by treating 2-(t-butyldimethylsilyl)-3-(hydroxymethyl)furan with 2.2 equivalents of n-butyllithium (DME/0°C/15 min), is trapped by a variety of electrophiles to produce, after desilylation, 3,4-disubstituted furans in good to moderate yields.

  通过用2.2当量的正丁基锂（DME / 0°C /在15分钟内）被各种亲电试剂捕获，去甲硅烷基化后可产生3,4-二取代的呋喃，产率中等至中等。
• 10.3762/bjoc.20.88
  作者：Eggly, Alyssa S.、Otgontseren, Namuunzul、Roberts, Carson B.、Alwali, Amir Y.、Hennigan, Haylie E.、Parkinson, Elizabeth I.

  DOI：10.3762/bjoc.20.88

  日期：——

  chromatography–mass spectrometry (LC–MS). The molecular probe, which undergoes this reaction with a variety of furans, was designed with both a UV-tag and a mass tag to enable easy identification. The probe has been tested with a variety of purified furans, including natural products, methylenomycin furan (MMF) hormones, and MMF derivatives. Moreover, the molecular probe has been tested in crude supernatants

   抽象的 天然产物 (NP) 是新型药物的绝佳灵感来源，通常针对感兴趣的靶标表现出独特的生物活性。具体来说，含有呋喃部分的纳米粒子显示出对抗多种疾病的活性，包括真菌感染和癌症。然而，从细胞上清液中发现和分离这些小分子具有挑战性。本文描述的工作展示了一种分子探针的开发，该探针可以通过 [4 + 2] Diels-Alder 环加成共价修饰呋喃部分，使它们可以通过液相色谱-质谱 (LC-MS) 轻松识别。该分子探针与多种呋喃发生反应，设计有紫外线标签和质量标签，以便于识别。该探针已使用多种纯化呋喃进行了测试，包括天然产物、亚甲霉素呋喃 (MMF) 激素和 MMF 衍生物。此外，该分子探针已在各种链霉菌菌株的粗上清液中进行了测试，并且能够鉴定 MMF。 Beilstein J. Org. Chem. 2024, 20, 1001–1010. doi:10.3762/bjoc.20.88
• Regioselective Preparation of 2,4-, 3,4-, and 2,3,4-Substituted Furan Rings. 2.¹ Regioselective Lithiation of 2-Silylated-3-substituted Furan Rings
  作者：Edward Bures、James A. Nieman、Shuyuan Yu、Patrick G. Spinazzé、Jean-Louis J. Bontront、Ian R. Hunt、Arvi Rauk、Brian A. Keay

  DOI：10.1021/jo971098b

  日期：1997.12.1

  A new method for the preparation of 3,4- and 2,5-disubstituted furan rings is described. A variety of 2-silylated-3-(hydroxymethyl)furans and 2-silylated-3-furoic acids lithiate exclusively at C-4 when treated with 2.2 equivs of BuLi. The resulting dianions were quenched with a variety of electrophiles to provide 2-silylated-3-(hydroxymethyl)-substituted furans and 2-silylated-4-substituted 3-furoic acids in good to excellent yields. Removal of the silyl group (n-Bu4NF) provided a variety of 4-substituted-3-(hydroxymethyl)furans and methyl 4-substituted-3-furoates, respectively. The latter esters were prepared due to difficulties encountered in isolating 4-substituted-3-furoic acids. The site of lithiation was altered by protecting the 3-hydroxyl group with a triethylsilane. Lithiation of 2-silylated-3-(((triethylsilyl)oxy)methyl)furan with 1.2 equivs of BuLi followed by the addition of electrophiles provided 2-silylated-3-(((triethylsilyl)oxy)methyl)-5-substituted furan rings. Subsequent removal of both silyl groups provided 2,4-disubstituted furan rings in moderate to good yields. A rationale is provided to explain why protection of the hydroxyl group at C-3 leads to a change in lithiation from the C-4 to the C-5 position of the furan ring. In addition, an explanation for the observed effect of adding HMPA or LiCl to the solution during the lithiation of 2-(tert-butyldimethylsilyl)-3-(hydroxymethyl)furan is provided.