5-Methoxy-1,2,3,4-tetrahydrospiro<1,3>dioxine> | 207504-79-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: 5-Methoxy-1,2,3,4-tetrahydrospiro<1,3>dioxine>
• 英文别名: (2H)-5-methoxy-2,3-dihydrospiro[naphthalene-1(4H),2'-naphtho[1,8-de][1,3]dioxin]；5-Methoxy-3,4-dihydro-2H-spiro[naphthalene-1,2'-naphtho[1,8-de][1,3]dioxine]；8-methoxyspiro[2,3-dihydro-1H-naphthalene-4,3'-2,4-dioxatricyclo[7.3.1.05,13]trideca-1(12),5,7,9(13),10-pentaene]
• CAS: 207504-79-8
• 化学式: C₂₁H₁₈O₃
• 分子量: 318.372
• InChiKey: HMXDHLYUXLIQNP-UHFFFAOYSA-N

物化性质

• 熔点：
  155 °C
• 沸点：
  525.1±50.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  24
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5-Methoxy-1,2,3,4-tetrahydrospiro<1,3>dioxine> 在 叔丁基过氧化氢 、 氢氧化钾 、 (+)-β-chlorodiisopinocampheylborane 、 CrO₃*HCl*biPy 、 双氧水 、 magnesium iodide 作用下， 以 苯 为溶剂， 反应 29.5h， 生成 CJ-12,371
  参考文献：
  名称：

  Total syntheses of palmarumycins CP1 and CP2 and CJ-12,371: novel spiro-ketal fungal metabolites

  摘要：

  报告了掌菌素CP1 1和CP2 9以及结构相关的CJ-12,371 11的总合成，从而建立了一种合成掌菌素、二氧烷及普鲁索梅林类天然产物的策略。

  DOI：

  10.1039/a800237a
• 作为产物：
  描述：

  1,8-萘磺酸内酯 在 氢氧化钾 、 硫酸 作用下， 以 甲苯 为溶剂， 反应 72.5h， 生成 5-Methoxy-1,2,3,4-tetrahydrospiro<1,3>dioxine>
  参考文献：
  名称：

  The synthesis of 1,8-dihydroxynaphthalene-derived natural products: palmarumycin CP1, palmarumycin CP2, palmarumycin C11, CJ-12,371, deoxypreussomerin A and novel analogues

  摘要：

  文章介绍了利用 1,8-二羟基萘进行初步缩醛化，然后再对环 A 功能进行详细阐述的路线，对标题真菌代谢物进行了全合成。此外还报告了新的类似物。对棕榈霉素 C11、联苯霉素和 Sch 53,823 的结构进行了澄清。

  DOI：

  10.1039/a901076i

文献信息

• Unified Route to the Palmarumycin and Preussomerin Natural Products. Enantioselective Synthesis of (−)-Preussomerin G
  作者：Anthony G. M. Barrett、Frank Blaney、Andrew D. Campbell、Dieter Hamprecht、Thorsten Meyer、Andrew J. P. White、David Witty、David J. Williams

  DOI：10.1021/jo0110247

  日期：2002.5.1

  inhibitor (-)-preussomerin G has been synthesized, achieving the first enantioselective route for accessing this family of natural products. Highlights of the synthetic work include an asymmetric epoxidation of a cyclic enone in excellent yield and enantiomeric excess and a potentially biomimetic oxidative spirocyclization for the introduction of the bis-spiroketal array unique to the preussomerin natural

  通过鉴定出其中三种天然产物的绝对立体化学，已经实现了八烷基金霉素家族的八个成员的总合成。另外，已经合成了ras-法呢基转移酶抑制剂（-）-前体小体G，实现了获得该天然产物家族的第一对映选择性途径。合成工作的重点包括以极佳的收率和对映异构体过量进行环状烯酮的不对称环氧化，以及潜在的仿生氧化螺环化反应，以引入早螺旋体天然产物所独有的双螺酮阵列。
• Total synthesis of Palmarumycin BGs, C₁ and Guignardin E
  作者：Xinlei Liu、Shuyi Li、Xinyu Wei、Yu Zhao、Daowan Lai、Ligang Zhou、Mingan Wang

  DOI：10.1039/c9ra10316c

  日期：——

  Palmarumycin C2 through a N-benzyl cinchoninium chloride-catalyzed epoxidation, an organoselenium-mediated reduction, and a cerium(III) chloride hydrate-promoted regioselective ring-opening and elimination of cyclic α,β-epoxy ketone as the key steps via 6–7 step routes using 1,8-dihydroxynaphthalene (DHN) and 5-methoxytetralone as the starting materials in overall yields of 1.0–17.4%, respectively. Their structures

  Palmarumycin BG1-3、BG5-6、C 1和 Guignardin E ( 1-7 ) 的首次全合成是由相同的中间体 Palmarumycin C 2通过N-苄基辛可宁氯化物催化的环氧化反应（一种有机硒介导的还原反应）实现的，以及以1,8-二羟基萘 (DHN) 和 5-甲氧基四氢萘酮为起始，通过6-7步路线，以氯化铈 ( III ) 水合物促进区域选择性开环和消除环状 α,β-环氧酮为关键步骤材料的总产率分别为 1.0-17.4%。它们的结构和绝对构型由1 H、13表征和确定 C NMR、IR、HR-ESI-MS 和 X 射线衍射数据。这些化合物对 HCT116、U87-MG、HepG2、BGC823 和 PC9 细胞系表现出显着的抑制活性。
• Benzylic Oxidation Catalyzed by Dirhodium(II,III) Caprolactamate
  作者：Arthur J. Catino、Jason M. Nichols、Hojae Choi、Sidhartha Gottipamula、Michael P. Doyle

  DOI：10.1021/ol0520020

  日期：2005.11.1

  Dirhodium caprolactamate [Rh-2(cap)(4)] is an effective catalyst for benzylic oxidation with tert-butyl hydroperoxide (TBHP) under mild conditions. Sodium bicarbonate is the optimal base additive for substrate conversion. Benzylic carbonyl compounds are readily obtained, and a formal synthesis of palmarumycin CP2 using this methodology is described.
• Syntheses of palmarumycin CP1 and CP2, CJ-12,371 and novel analogues
  作者：Jacques P Ragot、Marie-Lyne Alcaraz、Richard J.K Taylor

  DOI：10.1016/s0040-4039(98)00896-x

  日期：1998.7

  Total syntheses of the title fungal metabolites are described via a route which utilises initial acetalisation with 1,8-dihydroxynaphthalene followed by elaboration of the ring A functionality. Novel analogues are also reported. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Elucidation of Palmarumycin Spirobisnaphthalene Biosynthesis Reveals a Set of Previously Unrecognized Oxidases and Reductases
  作者：Siji Zhao、Zhen Shen、Ziqi Zhai、Ruya Yin、Dan Xu、Mingan Wang、Qi Wang、You-Liang Peng、Ligang Zhou、Daowan Lai

  DOI：10.1002/anie.202401979

  日期：——

  Spirobisnaphthalenes (SBNs) are a class of highly oxygenated, fungal bisnaphthalenes containing an unique spiroketal bridge, that displayed diverse bioactivities. Among the reported SBNs, palmarumycins are the major type, which are precursors for the other type of SBNs structurally. However, the biosynthesis of SBNs is unclear. In this study, we elucidated the biosynthesis of palmarumycins, using gene disruption, heterologous expression, and substrate feeding experiments. The biosynthetic gene cluster for palmarumycins was identified to be distant from the polyketide synthase gene cluster, and included two cytochrome P450s (PalA and PalB), and one short chain dehydrogenase/reductase (PalC) encoding genes as key structural genes. PalA is an unusual, multifunctional P450 that catalyzes the oxidative dimerization of 1,8‐dihydroxynaphthalene to generate the spiroketal linkage and 2,3‐epoxy group. Chemical synthesis of key intermediate and in vitro biochemical assays proved that the oxidative dimerization proceeded via a binaphthyl ether. PalB installs the C‐5 hydroxyl group, widely found in SBNs. PalC catalyzes 1‐keto reduction, the reverse 1‐dehydrogenation, and 2,3‐epoxide reduction. Moreover, an FAD‐dependent oxidoreductase, encoded by palD, which locates outside the cluster, functions as 1‐dehydrogenase. These results provided the first genetic and biochemical evidence for the biosynthesis of palmarumycin SBNs.