8-hydroxy-4H-spiro[naphthalene-1,2′-[1,3]dioxolan]-4-one | 1449236-74-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 8-hydroxy-4H-spiro[naphthalene-1,2′-[1,3]dioxolan]-4-one
• 英文别名: 5'-Hydroxyspiro[1,3-dioxolane-2,4'-naphthalene]-1'-one；5'-hydroxyspiro[1,3-dioxolane-2,4'-naphthalene]-1'-one
• CAS: 1449236-74-1
• 化学式: C₁₂H₁₀O₄
• 分子量: 218.209
• InChiKey: ZBRIQGXUZPCSNJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  8-hydroxy-4H-spiro[naphthalene-1,2′-[1,3]dioxolan]-4-one 在 盐酸 、 lithium aluminium tetrahydride 、 碘苯二乙酸 、 potassium tert-butylate 、 甲铝双(2,6-二叔丁基-4-苯甲醚) 、 碳酸氢钠 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 、 乙酸乙酯 为溶剂， 生成
  参考文献：
  名称：

  Selective Introduction of Four Contiguous Stereocenters on the B-Ring of 4-Hydroxyzinowol

  摘要：

  4-Hydoxyzinowol is a bioactive polyoxygenated dihydro-beta-agarofuran sesquiterpenoid. Here we describe construction of four contiguous cis-oriented stereocenters on the B-ring of 4-hydroxyzinowol. Introduction of a C7-isopropenyl group by the 1,4-addition of isopropenyl magnesium bromide was effectively assisted by methyl aluminum bis(2,6-di-tert-butyl-4-methylphenoxide). Taking advantage of the presence of the C7-substituent, three hydroxy groups were installed in a stereoselective fashion at the C6, 8 and 9 positions. In this study, we employed a new reagent combination of Sc(OTf)(3) and Zn(OTf)(2) for the hydrolysis of the cyclic acetal on the rigid oxabicyclo[3.2.1]octane structure.

  DOI：

  10.3987/com-12-s(n)76
• 作为产物：
  描述：

  1,5-二羟基萘 在 吡啶 、 4-二甲氨基吡啶 、 lithium hydroxide monohydrate 、 1,5-二羟基萘 、 sodium methylate 、 [双(三氟乙酰氧基)碘]苯 作用下， 以 四氢呋喃 、 水 、 甲苯 、 乙腈 为溶剂， 反应 35.0h， 生成 8-hydroxy-4H-spiro[naphthalene-1,2′-[1,3]dioxolan]-4-one
  参考文献：
  名称：

  萘环素类化合物：通过硫醇盐介导的环化与双环[3.2.1]辛二烯酮双连接的八肽二聚体

  摘要：

  报道了一种在天然存在的octaketide二聚体中合成双环[3.2.1]辛二烯酮支架的可行方法。该方法采用由不寻常的乙二硫醇单钠盐介导的还原环化反应。

  DOI：

  10.1002/anie.201503442

文献信息

• Enantioselective Access to Bicyclo[3.2.1]octadienone Skeleton: Total Syntheses of (+)-Engelharquinone and Its Epoxide
  作者：Takumi Fukazawa、Yoshio Ando、Ken Ohmori、Tamio Hayashi、Keisuke Suzuki

  DOI：10.1021/acs.orglett.7b00464

  日期：2017.3.17

  The first enantioselective total syntheses of engelharquinone (2) and its epoxide 3 have been achieved. The key steps include (1) catalytic asymmetric 1,4-addition of a naphthylboronic acid derivative to a masked naphthoquinone derivative by using a chiral Rh-complex and (2) thiolate-promoted stereospecific construction of the bicyclo[3.2.1]octadienone scaffold.

  已经实现了恩格尔哈醌（2）及其环氧化物3的第一对映选择性全合成。关键步骤包括（1）通过使用手性Rh-络合物将萘基硼酸衍生物催化不对称1,4-加成到掩蔽的萘醌衍生物上，以及（2）硫醇盐促进的双环[3.2.1]十八烯酮骨架的立体有择结构。 。
• Total Synthesis of (−)-4-Hydroxyzinowol
  作者：Hidenori Todoroki、Masafumi Iwatsu、Daisuke Urabe、Masayuki Inoue

  DOI：10.1021/jo501666x

  日期：2014.9.19

  were then introduced by oxidative dearomatization and Diels–Alder reaction, respectively. After acid-promoted formation of the C-ring ether, the C1-, 2-, 4- and 6-oxygen-based functional groups were stereoselectively installed to deliver the fully functionalized tricycle. Finally, the polyhydroxylated structure was converted to the polyacylated target molecule 1 via regioselective acetylation and benzoylation

  （-）-4-Hydroxyzinowol（1）是一种强力的P糖蛋白抑制剂，在癌症治疗中与多种药物耐药有关。的高度氧化结构1包括一反-decalin（AB环）和四氢呋喃（C形环）和具有6个酰氧基，一个羟基和一个烷氧基。合成1的挑战10碳十氢萘骨架上的九个连续的立体生成中心尤其突出了这一点。通过明智地应用强大的化学和立体选择反应，可以从5-乙酰氧基萘-1-醇以36个步骤完成这种极其复杂的结构的总合成。铑催化的异丙烯基的不对称1,4-加成可确定C7-立体中心，其余三个为顺式以逐步的方式立体选择性地构造B环的-取向羟基（C6、8和9）。然后分别通过氧化脱芳香化作用和Diels-Alder反应引入AB环交界处的C5-四取代碳和C10-季碳。酸促进C环醚的形成后，立体选择性地安装基于C1、2、4和6氧的官能团，以提供完全官能化的三环。最后，通过区域选择性乙酰化和苯甲酰化将多羟基化的结构转化为多酰化的靶分子1。
• Thiolate-mediated reductive cyclization: asymmetric total synthesis of (+)-engelharquinone
  作者：Yoshio Ando、Takumi Fukazawa、Subaru Hori、Ken Ohmori、Keisuke Suzuki

  DOI：10.1080/10426507.2019.1603718

  日期：2019.7.3

  Abstract We report herein the asymmetric total synthesis of (+)-engelharquinone and its epoxide by exploiting two key reactions; (1) Rhodium catalyzed asymmetric 1,4-addition and (2) thiolate-mediated reductive cyclization. Graphical Abstract

  摘要 我们在此报告了 (+)-engelharquinone 及其环氧化物的不对称全合成，利用两个关键反应；(1) 铑催化不对称 1,4-加成和 (2) 硫醇盐介导的还原环化。图形概要
• Toward Naphthocyclinones: Doubly Connected Octaketide Dimers with a Bicyclo[3.2.1]octadienone Core by Thiolate-Mediated Cyclization
  作者：Yoshio Ando、Subaru Hori、Takumi Fukazawa、Ken Ohmori、Keisuke Suzuki

  DOI：10.1002/anie.201503442

  日期：2015.8.10

  A viable method is reported for the synthesis of the bicyclo[3.2.1]octadienone scaffold in naturally occurring octaketide dimers. The procedure employs a reductive cyclization reaction mediated by an unusual ethanedithiol monosodium salt.

  报道了一种在天然存在的octaketide二聚体中合成双环[3.2.1]辛二烯酮支架的可行方法。该方法采用由不寻常的乙二硫醇单钠盐介导的还原环化反应。
• Selective Introduction of Four Contiguous Stereocenters on the B-Ring of 4-Hydroxyzinowol
  作者：Masayuki Inoue、Masafumi Iwatsu、Daisuke Urabe、Hidenori Todoroki、Kengo Masuda

  DOI：10.3987/com-12-s(n)76

  日期：——

  4-Hydoxyzinowol is a bioactive polyoxygenated dihydro-beta-agarofuran sesquiterpenoid. Here we describe construction of four contiguous cis-oriented stereocenters on the B-ring of 4-hydroxyzinowol. Introduction of a C7-isopropenyl group by the 1,4-addition of isopropenyl magnesium bromide was effectively assisted by methyl aluminum bis(2,6-di-tert-butyl-4-methylphenoxide). Taking advantage of the presence of the C7-substituent, three hydroxy groups were installed in a stereoselective fashion at the C6, 8 and 9 positions. In this study, we employed a new reagent combination of Sc(OTf)(3) and Zn(OTf)(2) for the hydrolysis of the cyclic acetal on the rigid oxabicyclo[3.2.1]octane structure.