1,2-dimethoxy-13H-[1,3]dioxolo[4',5':4,5]benzo[1,2-h]benzo[c]chromene-13-one | 64666-98-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并吡喃类
• 英文名称: 1,2-dimethoxy-13H-[1,3]dioxolo[4',5':4,5]benzo[1,2-h]benzo[c]chromene-13-one
• 英文别名: 1,2-dimethoxy-13H-[1,3]dioxolo[4',5':4,5]benzo[1,2-h]benzo[c]chromen-13-one；6,7-dimethoxy-3,4-methylenedioxy-6H-naphtho[1,2-b]benzo[d]pyran-6-one；7,8-dimethoxy-2,3-methylenedioxy-6H-benzo[d]naphtho[1,2-b]pyran-6-one；7,8-dimethoxy-2,3-methylenedioxy-6H-naphtho[1,2-b]benzo[d]pyran-6-one；1,2-dimethoxy-8,10,12-trioxacyclopenta[b]chrysen-13-one；arnottin I；17,18-dimethoxy-5,7,21-trioxapentacyclo[11.8.0.02,10.04,8.014,19]henicosa-1(13),2,4(8),9,11,14(19),15,17-octaen-20-one
• CAS: 64666-98-4
• 化学式: C₂₀H₁₄O₆
• 分子量: 350.328
• InChiKey: AOYQXCYLRJFNFX-UHFFFAOYSA-N

物化性质

• 熔点：
  299-300 °C(Solv: chloroform (67-66-3))
• 沸点：
  586.3±50.0 °C(Predicted)
• 密度：
  1.418±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,2-dimethoxy-13H-[1,3]dioxolo[4',5':4,5]benzo[1,2-h]benzo[c]chromene-13-one 在 lithium hydroxide monohydrate 、 盐酸 、 [双(三氟乙酰氧基)碘]苯 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 15.0h， 以56%的产率得到arnottin II
  参考文献：
  名称：

  Syntheses of Arnottin I and Arnottin II

  摘要：

  Short total syntheses of arnottin I and II were accomplished in 5 and 6 steps, respectively. A sesamol-benzyne cycloaddition with a 3-furyl-benzoate followed by regiospecific lactonization provided rapid, large-scale access to the core of arnottin I. Saponification of arnottin I and hypervalent iodide mediated spirocyclization provided an efficient and direct preparation of racemic arnottin II.

  DOI：

  10.1021/acs.joc.5b00107
• 作为产物：
  描述：

  1,2-二(苄氧基)-4,5-二溴苯 在 palladium on activated charcoal 正丁基锂 、 dibromo[1,2-bis(diphenylphosphino)ethane]nickel(II) 、 氢气 、 三乙胺 、 锌 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 反应 27.0h， 生成 1,2-dimethoxy-13H-[1,3]dioxolo[4',5':4,5]benzo[1,2-h]benzo[c]chromene-13-one
  参考文献：
  名称：

  Nickel-Catalyzed Synthesis of Benzocoumarins:  Application to the Total Synthesis of Arnottin I

  摘要：

  The ring-opening addition of methyl 2,3-dimethoxy-6-iodobenzoate to oxabenzonorbornadienes followed by cyclization in the presence of NiBr2( dppe) and Zn metal powder in acetonitrile at 80 C to give the corresponding benzocoumarin derivatives is described. This methodology was then applied to the synthesis of natural product arnottin I, first isolated from Xanthoxylum arnottianum Maxim, using protecting group chemistry. After deprotection and subsequent ring closure, arnottin I was obtained in 21% overall yield after six steps starting from catechol.

  DOI：

  10.1021/jo061477h

文献信息

• Concise Synthesis of Arnottin I and (−)-Arnottin II
  作者：Fujiko Konno、Tsutomu Ishikawa、Masatoshi Kawahata、Kentaro Yamaguchi

  DOI：10.1021/jo061905j

  日期：2006.12.1

  with a fused tetracyclic system. Aromatization of the 7,8-dimethoxy-2,3-methylenedioxy derivative yielded arnottin I, whereas oxidation with dioxirane afforded dihydroarnottin II composed of a spiro phthalide−tetralone system. Sharpless asymmetric dihydroxylation using AD-mix yielded optically active dihydroarnottin II with good enantioselectivity. The absolute stereochemistry of the stereogenic center

  将布赫瓦尔德方案应用于邻溴苯甲酸酯和1-四氢萘酮的偶联，直接得到具有稠合四环系统的苯并二氢萘并吡喃酮。7,8-二甲氧基-2,3-亚甲二氧基衍生物的芳构化反应产生了arnottin I，而用二环氧乙烷氧化则得到了由螺邻苯二甲酰-四氢萘酮体系组成的二氢芳构化蛋白II。使用AD-mix进行无尖锐的不对称二羟基化反应，得到具有良好对映选择性的旋光性二氢芳构蛋白II。通过二溴衍生物的X-射线晶体学分析确定（+）-螺旋产物中的立体中心的绝对立体化学为R。使（+）-二氢阿诺汀II连续溴化和脱氢溴化以制备（-）-阿诺丁II。在[R通过不对称合成证实了天然（-）-芳构蛋白II的-构型，该构型先前通过应用激子手性方法分配给CD光谱中观察到的棉花效应。
• Asymmetric dearomative spirolactonization of naphthols using λ3-iodanes under chiral phase-transfer catalysis
  作者：Kevin Antien、Guillaume Viault、Laurent Pouységu、Philippe A. Peixoto、Stéphane Quideau

  DOI：10.1016/j.tet.2017.04.028

  日期：2017.6

  The asymmetric phase-transfer catalytic effect of chiral Cinchona alkaloid-derived quaternary ammonium salts was investigated in the context of the λ3-iodane-mediated dearomative spirolactonization of naphthols. The scope and limitations of this methodology were evaluated using various substrates, which were converted into spirolactones in good yields and with enantiomeric excesses up to 58%.

  手性的不对称相转移催化效果金鸡纳生物碱类季铵盐在λ的情况下进行了研究3萘酚的-iodane介导dearomative spirolactonization。使用各种底物评估了该方法的范围和局限性，这些底物以良好的产率转化为螺内酯，对映体过量最高可达58％。
• Benzannulation for the Regiodefined Synthesis of 2-Alkyl/Aryl-1-naphthols: Total Synthesis of Arnottin I
  作者：Dipakranjan Mal、Amit Kumar Jana、Prithiba Mitra、Ketaki Ghosh

  DOI：10.1021/jo2003677

  日期：2011.5.6

  The annulation of phthalides with α-alkyl/arylacrylates in the presence of LDA/LHMDS is shown to directly give alkyl/aryl-1-naphthols. The method involving a novel dealkoxycarbonylation obviates the regiochemical issues in the synthesis of polysubstituted naphthalenes, and it forms the key step in a three-step total synthesis of arnottin I, a naphthobenzopyranone natural product.

  显示在LDA / LHMDS存在下，邻苯二甲酸酯与α-烷基/芳基丙烯酸酯的环化反应可直接得到烷基/芳基-1-萘。涉及新型脱烷氧羰基化的方法消除了多取代萘合成中的区域化学问题，它构成了三步骤全合成Arnottin I（萘并苯并吡喃酮天然产物）的关键步骤。
• Synthesis of [N,P] ligands based on pyrrole. Application to the total synthesis of arnottin I
  作者：Jesús V. Suárez-Meneses、Edgar Bonilla-Reyes、Ever A. Blé-González、M. Carmen Ortega-Alfaro、Rubén Alfredo Toscano、Alejandro Cordero-Vargas、José G. López-Cortés

  DOI：10.1016/j.tet.2014.01.002

  日期：2014.2

  This paper describes the synthesis of a new class of [N,P] ligands based on pyrrole with a dimethylamino group as hard donor and a phosphine moiety as soft base. We have also modified the phosphine fragment to change the electronic and steric properties of these ligands. Palladium complex 3a proved to be very efficient in Heck cross-coupling reactions and in intramolecular aryl–aryl couplings of esters

  本文描述了基于吡咯的新型[N，P]配体的合成，其中二甲氨基为硬供体，膦部分为软碱。我们还修饰了膦片段，以改变这些配体的电子和位阻性质。事实证明，钯配合物3a在Heck交叉偶联反应以及酯和酰胺的分子内芳基-芳基偶联中非常有效。我们已经证明了这种新型催化剂在天然产物芦丁素I的全合成中的适用性和效率。
• Synthesis of Arnottin I through a Palladium-Mediated Aryl-Aryl Coupling Reaction.
  作者：Takashi HARAYAMA、Hirotake YASUDA、Toshihiko AKIYAMA、Yasuo TAKEUCHI、Hitoshi ABE

  DOI：10.1248/cpb.48.861

  日期：——

  6H-Dibenzo[b,d]pyran-6-one, 6H-benzo[d]naphtho[1,2-b]pyran-6-one, and their derivatives were prepared via the palladium mediated aryl-aryl coupling reaction of aryl ortho-halobenzoate. The short step synthesis of arnottin I(1) was achieved by this method.

  6H-二苯并[b，d]吡喃-6-一，6H-苯并[d]萘并[1,2-b]吡喃-6-及其衍生物是通过钯介导的芳基芳基-芳基偶联反应制备的邻卤代苯甲酸酯。通过这种方法可以实现Arnottin I（1）的短时合成。