1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione | 50874-38-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione
• 英文别名: (1R,2R,7S,8S)-1,8,9,10-tetrachloro-11,11-dimethoxytricyclo[6.2.1.02,7]undeca-4,9-diene-3,6-dione
• CAS: 50874-38-9
• 化学式: C₁₃H₁₀Cl₄O₄
• 分子量: 372.032
• InChiKey: DCGCFQBJRLWZID-ZTCHHREXSA-N

物化性质

• 沸点：
  426.0±45.0 °C(Predicted)
• 密度：
  1.63±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione 在 双氧水 、 sodium methylate 、 碳酸氢钠 作用下， 以 甲醇 、 乙醚 、 丙酮 为溶剂， 反应 1.17h， 生成 5,6,7,8-tetrachloro-2-methoxy-5,8-dimethoxymethano-4a,5,8,8a-tetrahydro-1,4-naphthoquinone
  参考文献：
  名称：

  Cage compounds. Part 1. Base-promoted reaction of 5,6,7,8-tetrachloro-5,8-dimethoxymethano-4a,5,8,8a-tetrahydro-1,4-naphthoquinone epoxide

  摘要：

  DOI：

  10.1021/jo00247a033
• 作为产物：
  描述：

  5,5-二甲氧基-1,2,3,4-四氯环戊二烯 、 对苯醌 以 甲苯 为溶剂， 反应 24.0h， 以83%的产率得到1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione
  参考文献：
  名称：

  追求五边形十二面体的实验：凸聚喹烷的模型合成

  摘要：

  在制备 le precurseur de symmetrie C 2 , la 四环 [7.2.1.0 4,11 .0 6,10 ] dodecadiene-2,7dione-5,12

  DOI：

  10.1021/ja00311a049

文献信息

• Pd(II)-Catalyzed Enantioselective Desymmetrization of Polycyclic Cyclohexenediones: Conjugate Addition versus Oxidative Heck
  作者：Claire J. C. Lamb、Filipe Vilela、Ai-Lan Lee

  DOI：10.1021/acs.orglett.9b03293

  日期：2019.11.1

  Pd(II)-catalyzed desymmetrization of polycyclic cyclohexenediones has been achieved with high enantio- and diastereoselectivities. Up to five contiguous stereocenters are desymmetrized, while simultaneously, an additional stereocenter is created by the enantioselective conjugate addition. Surprisingly, the conjugate addition products dominate even under typical oxidative Heck conditions, and these

  Pd（II）催化的多环环己二烯键不对称反应具有很高的对映选择性和非对映选择性。取消对称化多达五个连续的立体中心，同时，通过对映选择性共轭加法创建另一个立体中心。出乎意料的是，即使在典型的氧化赫克条件下，缀合物加成产物仍占主导地位，这些观察结果可能提供对两个相关反应之间竞争的一些见解。
• Polycyclitols — Novel conduritol and carbasugar hybrids as new glycosidase inhibitors
  作者：Goverdhan Mehta、Senaiar S Ramesh

  DOI：10.1139/v05-032

  日期：2005.6.1

  A family of novel carbasugar analogues (bicyclitols) based on cis-hydrindane and cis-decalin frameworks has been conceptualized. These novel entities can be regarded as conduritol and carbasugar hybrids. Syntheses of these polyhydroxylated entities have been achieved in stereo- and regioselective manners, starting from the readily available Diels–Alder adducts of 5,5-dimethoxy-1,2,3,4-tetrachlorocyclopentadiene and appropriate dienophiles like cyclopentadiene or p-benzoquinone, that embody a masked 7-ketonorbornenone moiety. Thermally induced chelotropic elimination of CO from the appropriately functionalized 7-ketonorbornenone derivatives to deliver annulated bicyclic 1,3-cyclohexadiene derivatives was the key step in this synthetic endeavor. Further oxy-functionalization of the 1,3-cyclohexadiene moiety delivered the targeted polycyclitols. A preliminary investigation of the glycosidase inhibitory potency of these bicyclitols, identified compounds 18 and 54 as potent and selective inhibitors of α-glucosidase (yeast).Key words: carbasugar, conduritol, glycomimics, glycosidase inhibitors.

  一系列基于顺式-水合甘氨酸和顺式-癸烷骨架的新型碳糖类似物（双环醇）已被构想出来。这些新型实体可以被视为康杜糖和碳糖的混合体。这些多羟基实体的合成已经以立体选择性和区域选择性的方式实现，从易得的5,5-二甲氧基-1,2,3,4-四氯环戊二烯的Diels-Alder加合物开始，以及类似环戊二烯或对苯二醌的适当双烯作为二烯体，这些二烯体包含一个掩蔽的7-酮诺邦酮基团。从适当官能化的7-酮诺邦酮衍生物中通过热诱导的螯合消除CO来提供环化双环1,3-环己二烯衍生物是这一合成努力的关键步骤。进一步对1,3-环己二烯基团进行氧功能化，形成目标多环醇。对这些双环醇的糖苷酶抑制活性进行初步研究，鉴定出化合物18和54作为α-葡萄糖苷酶（酵母）的有效和选择性抑制剂。关键词：碳糖，康杜糖，糖类似物，糖苷酶抑制剂。
• Benzoannulation of Quinones by a Cycloaddition-Fragmentation Approach. A Simple Synthesis of Methoxycarbonyl-Substituted Polyacenoquinones
  作者：Teh-Chang Chou、Chia-Jung Hsu、Jao-Yu Chen

  DOI：10.1002/jccs.200400025

  日期：2004.2

  Diels-Alder cycloadditions of 1,2,3,4-tetrachloro-4,5-dimethoxycyclopentadiene (1) with p-benzoquinone (2), 1,4-naphthoquinone (3), 1,4-anthraquinone (4), and 2,3-dicyano-1,4-benzoquinone (5) were subjected to the reaction with triethylamine in dichloromethane at room temperature. Cycloadducts 2A and 5A enolized to give the corresponding hydroquinones 2B and 5B, which were oxidized with DDQ to afford naphthoquinone

  从 1,2,3,4-四氯-4,5-二甲氧基环戊二烯 (1) 与对苯醌 (2)、1,4-萘醌 (3)、1 的 Diels-Alder 环加成反应得到的环加合物 2A-5A, 4-蒽醌(4)和2,3-二氰基-1,4-苯醌(5)在室温下在二氯甲烷中与三乙胺反应。环负载 2A 和 5A 烯醇化得到相应的对苯二酚 2B 和 5B，用 DDQ 氧化它们分别得到萘醌酯 2D 和蒽醌酯 5D。在环加合物 3A 和 4A 的情况下，烯醇化与氧化和裂解同时发生，分别直接产生聚苯醌酯 3D 和 4D。在相同的反应条件下，
• A Simple Procedure for Preparing Annulated<i>p</i>-Benzoquinones. Improved Synthesis of 1,4-Dihydro-1,4-methanonaphthalene-5,8-dione
  作者：Alan P. Marchand、Sulejman Alihodzic、Rajesh Shukla

  DOI：10.1080/00397919808005109

  日期：1998.2

  Abstract A simple and efficient two-step, one-pot synthesis of substituted 1,4-dihydro-1,4-methanonaphthalene-5,8-diones is reported. This synthesis, which utilizes readily available starting materials and inexpensive reagents, can be used to prepare 1a-1c in 70–90% overall yield. This procedure was extended successfully to prepare a more highly complex annulated p-benzoquinone i.e., 8.

  摘要 报道了一种简单高效的两步一锅法合成取代的 1,4-二氢-1,4-甲萘-5,8-二酮。这种合成使用容易获得的起始材料和廉价的试剂，可用于以 70-90% 的总产率制备 1a-1c。该程序成功扩展以制备更复杂的环状对苯醌，即 8。
• Catalytic Enantioselective <i>de novo</i> Construction of Chiral Arenes through Desymmetrizing Oxidative [4+2]‐Cycloaddition
  作者：Biki Ghosh、Mahesh Singh Harariya、Santanu Mukherjee

  DOI：10.1002/anie.202204523

  日期：2022.9.12

  A desymmetrization approach to centrally chiral unfunctionalized arenes is developed through the enantioselective de novo construction of the arene ring by oxidative [4+2]-cycloaddition of polycyclic meso-cyclohexenediones. Catalyzed by a diphenylprolinol silyl ether, this external oxidant-free protocol gives rise to diversely substituted chiral arenes with outstanding enantioselectivity (up to >99

  中心手性非官能化芳烃的去对称化方法是通过多环内消旋-环己烯二酮的氧化[4+2]-环加成对芳烃环的对映选择性从头构建来开发的。在二苯基脯氨醇甲硅烷基醚的催化下，这种无外部氧化剂的方案产生了具有出色对映选择性（高达 >99.0:0.1 er）的多种取代的手性芳烃。