5,6,13,13a-tetrahydro[1,3]dioxolo[4,5-g]isoquino[3,2-a]isoquinolin-8-one | 76177-40-7

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 原小檗碱生物碱及其衍生物
• 英文名称: 5,6,13,13a-tetrahydro[1,3]dioxolo[4,5-g]isoquino[3,2-a]isoquinolin-8-one
• 英文别名: (+/-)-gusanlung D；2,3-Methylenedioxyberbin-8-one；5,7-dioxa-13-azapentacyclo[11.8.0.02,10.04,8.015,20]henicosa-2,4(8),9,15,17,19-hexaen-14-one
• CAS: 76177-40-7
• 化学式: C₁₈H₁₅NO₃
• 分子量: 293.322
• InChiKey: PUJMLVRTJXBOER-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-benzoyl-6,7-methylenedioxy-1,2-dihydroisoquinoline-1-carbonitrile 在 氢氧化钾 、 sodium hydride 、 sodium cyanoborohydride 、 三氟乙酸 作用下， 以 乙醇 、 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.17h， 生成 5,6,13,13a-tetrahydro[1,3]dioxolo[4,5-g]isoquino[3,2-a]isoquinolin-8-one
  参考文献：
  名称：

  来自 Reissert的原小 ber碱 -化合物VIII [1]。恶唑基异喹啉类化合物，新型高效合成8-氧代小ber碱的产物

  摘要：

   可从 Reissert 化合物轻松获得的某些苄基恶唑基异喹啉酮可通过 三个步骤有效地获得8-氧代小pro碱。制备了一系列这些新的前体以及几种氧代小ber碱，并研究了该方法的范围和局限性。

  DOI：

  10.1007/s00706-003-0013-5

文献信息

• Carbene-catalyzed aerobic oxidation of isoquinolinium salts: efficient synthesis of isoquinolinones
  作者：Guanjie Wang、Wanyao Hu、Zhouli Hu、Yuxia Zhang、Wei Yao、Lin Li、Zhenqian Fu、Wei Huang

  DOI：10.1039/c8gc01488d

  日期：——

  transformation. This reaction features ambient air as the sole oxidant and oxygen source, a broad substrate scope, and excellent functional-group tolerance and proceeds under mild reaction conditions. Furthermore, a highly efficient synthesis of bioactive molecules and natural products including N-methylcrinasiadine, N-isopentylcrinasiadine, N-phenethylcrinasiadine, isoindolo[2,1-b]isoquinolin-5(7H)-one, PJ-34,

  成功实现了温和环保的卡宾催化的异喹啉鎓盐的好氧氧化。因此，有效地制备了各种异喹啉酮和菲啶酮类，收率良好至优异。机理研究表明，氮杂-布雷斯洛中间体的形成是该转变的关键步骤。该反应具有环境空气作为唯一的氧化剂和氧气源，广泛的底物范围以及出色的官能团耐受性的特点，并且可以在温和的反应条件下进行。此外，生物活性分子和天然产物，包括一种高效合成Ñ -methylcrinasiadine，Ñ -isopentylcrinasiadine，Ñ -phenethylcrinasiadine，异吲哚基[2,1- b完成了] isoquinolin -5（7 H）-1，PJ-34，rac-Gusanlung D，罗塞他星，8-氧代伪巴马汀和伊利福林B的合成。
• The Thionium/N-Acyliminium Ion Cyclization Cascade as a Strategy for the Synthesis of Azapolycyclic Ring Systems
  作者：Albert Padwa、Alex G. Waterson

  DOI：10.1016/s0040-4020(00)00861-9

  日期：2000.12

  thiophenyl lactams with BF3·2AcOH which resulted in the generation of an N-acyliminium ion. Cyclization of the iminium ion onto the tethered aromatic ring led to various azapolycyclic ring systems. A related cyclization sequence also occurred with amidosulfoxides that possess simple olefinic tethers. The method was applied toward the synthesis of a member of the protoberberine alkaloid family.

  通过将苯硫酚加到适当的链烯酸π键上，制备了一系列的氨基亚砜，随后使原位生成的酰氯与3,4-二甲氧基苯乙胺反应。在催化量的ZnI 2存在下，使用1-（二甲基-叔丁基甲硅烷氧基）-1-甲氧基乙烯在干燥的乙腈中进行硅诱导的这些氨基亚砜的Pummerer反应，并导致非常干净地形成2-硫代苯基取代的内酰胺。通过用BF 3 ·2AcOH处理最初形成的硫代苯基内酰胺，可实现亚胺离子芳族π-环化反应，从而产生N-酰亚胺离子。亚胺离子在束缚的芳香环上的环化导致各种氮杂多环系统。具有简单烯烃系链的氨基亚砜也发生了相关的环化顺序。该方法用于原小ber碱生物碱家族成员的合成。
• Pd(II)-Catalyzed Intramolecular Tandem Olefin Amidation/C–H Activation Protocol for the Syntheses of the Protoberberine Class of Natural Products
  作者：Dnyaneshwar N. Garad、Santosh B. Mhaske

  DOI：10.1021/acs.orglett.6b01868

  日期：2016.8.5

  activation protocol has been developed for the synthesis of an 8-oxoprotoberberine core. It was successfully applied for the syntheses of (±)-8-oxocanadine, (±)-8-oxotetrahydropalmitine, and (±)-8-oxostylopine, which can be easily converted to the respective protoberberine natural products. The short synthetic route demonstrated would be useful for the synthesis of a large number of natural products and

  已开发了一种Pd（II）催化的分子内串联烯烃酰胺化/ CH活化方案，用于合成8-氧代小ber碱核心。它已成功地用于合成（±）-8-氧卡西丁，（±）-8-氧四氢巴米汀和（±）-8-氧杂螺碱，它们可以轻松地转化为相应的原小ber碱天然产物。证明的短合成路线可用于合成大量天然产物和以小ber碱为原料的类似物。
• Synthesis of the Reported Protoberberine Gusanlung D
  作者：Narshinha Argade、Prasad Wakchaure、Srinivasan Easwar

  DOI：10.1055/s-0028-1088050

  日期：2009.5

  Starting from homopiperonylamine or phenethylamine with homophthalic anhydride or 3,4-methylenedioxyhomophthalic acid, respectively, facile syntheses of the reported structures of (±)-gusanlung D and (±)-isogusanlung D were accomplished via regioselective­ reductive dehydration of the corresponding homophthalimides followed by an intramolecular acid-catalyzed or radical cyclization pathway. Starting from the corresponding suitably ortho-halogenated homophthalimides, the syntheses of dehydrogusanlung and dehydroisogusanlung D were completed via regioselective reductive dehydration followed by an intramolecular Heck coupling reaction as the key steps. The analytical and spectral data obtained for all four synthetic compounds differed from the reported data for natural gusanlung D, and therefore the structural assignment of the natural product needs to be revised.

  分别从均哌酰基胺或苯乙胺与均苯二甲酸酐或 3,4-亚甲二氧基均苯二甲酸开始，通过相应均苯二甲酰亚胺的回归选择性还原脱水，然后通过分子内酸催化或自由基环化途径，轻松合成了所报道的 (±)-gusanlung D 和 (±)-isogusanlung D 结构。从相应的正交卤代均苯二甲酰亚胺开始，通过选择性还原脱水，然后以分子内 Heck 偶联反应为关键步骤，完成了脱氢古生隆和脱氢异古生隆 D 的合成。所有四种合成化合物的分析和光谱数据都与天然草珊瑚龙 D 的报告数据不同，因此需要对天然产物的结构分配进行修订。
• Total Syntheses of (±)-Gusanlung A, (±)-Gusanlung D and 8-Oxyberberrubine and the Uncertainty Concerning the Structures of (-)-Gusanlung A, (-)-Gusanlung D and 8-Oxyberberrubine
  作者：Surachai Nimgirawath、Phansuang Udomputtimekakul、Thitima Apornpisarn、Asawin Wanbanjob、Thongchai Taechowisan

  DOI：10.3390/molecules14020726

  日期：——

  (±)-Gusanlung A, 8-oxyberberrubine and (±)-gusanlung D have been synthesized by radical cyclisation of the corresponding 2-aroyl-1-methylenetetra- hydroisoquinolines. The 1H and 13C spectra of (-)-gusanlung D were found to be different from those of synthetic (±)-gusanlung D. Careful analyses of the 13C spectra of (–)-gusanlung A and natural 8-oxyberberrubine also cast doubt on the correctness of the structures previously assigned to these two compounds. (±)-Gusanlung A and (±)-gusanlung D were inactive against Staphylococcus aureus ATCC25932, Escherichia coli ATCC10536 and Candida albicans ATCC90028.

  (±)-Gusanlung A、8-oxyberberrubine 和 (±)-gusanlung D 是通过相应的 2-芳酰基-1-亚甲基四氢异喹啉的自由基环化合成的。对 (-)-gusanlung A 和天然 8-oxyberberrubine 的 13C 光谱进行仔细分析后，发现 (-)-gusanlung D 的 1H 和 13C 光谱与合成 (±)-gusanlung D 的光谱不同。(±)-Gusanlung A 和 (±)-Gusanlung D 对金黄色葡萄球菌 ATCC25932、大肠杆菌 ATCC10536 和白色念珠菌 ATCC90028 均无活性。