5-(3,4,5-Trimethoxy-phenyl)-8H-furo[3',4':6,7]naphtho[2,3-d][1,3]dioxol-6-one | 6258-41-9

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 芳基萘木脂素
• 英文名称: 5-(3,4,5-Trimethoxy-phenyl)-8H-furo[3',4':6,7]naphtho[2,3-d][1,3]dioxol-6-one
• 英文别名: dehydrodesoxypodophyllotoxin；deoxydehydropodophyllotoxin；5-(3,4,5-trimethoxy-phenyl)-8H-furo[3',4':6,7]naphtho[2,3-d][1,3]dioxol-6-one；5-(3,4,5-Trimethoxy-phenyl)-8H-furo[3',4';6,7]naphtho[2,3-d][1,3]dioxol-6-on；5-(3,4,5-trimethoxyphenyl)-8H-[2]benzofuro[5,6-f][1,3]benzodioxol-6-one
• CAS: 6258-41-9
• 化学式: C₂₂H₁₈O₇
• 分子量: 394.381
• InChiKey: SSVGOUAYPDYOAE-UHFFFAOYSA-N

物化性质

• 熔点：
  266 °C
• 沸点：
  603.4±55.0 °C(Predicted)
• 密度：
  1.366±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  5-(3,4,5-Trimethoxy-phenyl)-8H-furo[3',4':6,7]naphtho[2,3-d][1,3]dioxol-6-one 在 盐酸 、 甲醇 、 氢氧化钾 、 乙酰氯 作用下， 生成 dimethyl 6,7-(methylenedioxy)-1-(3,4,5-trimethoxyphenyl)-naphthalene-2,3-dicarboxylate
  参考文献：
  名称：

  Haworth et al., Journal of the Chemical Society, 1935, p. 1576,1580

  摘要：

  DOI：
• 作为产物：
  描述：

  去氧鬼臼毒素 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 生成 5-(3,4,5-Trimethoxy-phenyl)-8H-furo[3',4':6,7]naphtho[2,3-d][1,3]dioxol-6-one
  参考文献：
  名称：

  In vivo immunosuppressive activity of some cyclolignans

  摘要：

  Several podophyllotoxin-related cyclolignans, either lacking the lactone ring or the methylenedioxy grouping, have been prepared and evaluated for their immunosuppressive (IMS) activity in the mouse allogeneic MLR in vitro test and in the in vivo techniques Graft vs Host Reaction (GVHR) and Skin Grafting (SG). The results obtained show that three cyclolignans fairly prevent splenomegaly in comparison with control animals and also promoted tolerance to grafting, being the first time that the in vivo LMS activity of cyclolignas is reported. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0960-894x(97)10072-5

文献信息

• Regiocontrolled Benzannulation of Diaryl(<i>gem</i>-dichlorocyclopropyl)methanols for the Synthesis of Unsymmetrically Substituted α-Arylnaphthalenes:  Application to Total Synthesis of Natural Lignan Lactones
  作者：Yoshinori Nishii、Taichi Yoshida、Hirofumi Asano、Kazunori Wakasugi、Jun-ichi Morita、Yoshifumi Aso、Eri Yoshida、Jiro Motoyoshiya、Hiromu Aoyama、Yoo Tanabe

  DOI：10.1021/jo047751u

  日期：2005.4.1

  synthesis of highly substituted α-arylnaphthalene analogues has been developed utilizing Lewis acid-promoted regiocontrolled benzannulation of aryl(aryl‘)-2,2-dichlorocyclopropylmethanols (aryl ≠ aryl‘; abbreviated as AACMs). Both AACM diastereomers were easily prepared via highly stereoselective addition (>95/5) of ArLi to gem-dichlorocyclopropropyl aryl‘ ketones. The choice of Lewis acids determined

  利用路易斯酸促进的芳基（芳基）-2，2-二氯环丙基甲醇（芳基≠芳基；缩写为AACMs）的路易斯酸区域控制的苯环已开发出高取代的α-芳基萘类似物的有效合成方法。两种AACM非对映异构体都可以通过将ArLi高​​度立体选择性地加成（> 95/5）到宝石-dichlorocyclopropropyl aryl'ketones上来制备。路易斯酸的选择决定了本苯并环的环化区域选择性。TiCl 4和SnCl 4使用螯合途径，而甲硅烷基三氟甲磺酸盐使用非螯合途径以40-91％的产率提供不对称取代的区域异构α-芳基萘，具有中等至出色的区域选择性（TiCl 4或SnCl 4 ; > 99 / 1-3 / 1，TBDMSOTf；> 1 / 99-1 / 4）。因此，通过选择反应顺序的顺序或合适的催化剂，可将α-芳基或α-芳基'部分（辅助芳基）引入α-芳基萘。证明了本方法在不对称取代的天然木脂素内酯，justicidin
• Synthesis of Biarylsvia Palladium-Catalyzed [2+2+2] Cocyclization of Arynes and Diynes: Application to the Synthesis of Arylnaphthalene Lignans
  作者：Yoshihiro Sato、Takayuki Tamura、Atsushi Kinbara、Miwako Mori

  DOI：10.1002/adsc.200600587

  日期：2007.3.5

  palladium(0)-catalyzed [2+2+2] cocyclization of diynes and arynes was developed. By this [2+2+2] cocyclization, various arylnaphthalene derivatives, including a sterically hindered 2,2′-disubstituted-1,1′-binaphthyl, can be constructed by virtue of a variety of combinations of diynes and aryne precursors. Using this [2+2+2] cocyclization as a key step, the total syntheses of natural arylnaphthalene lignans, taiwanin

  开发了一种通过钯（0）催化二炔和芳烃的[2 + 2 + 2]共环化构建联芳基的新方法。通过这种[2 + 2 + 2]共环化，可以通过二炔和芳烃前体的各种组合来构建各种芳基萘衍生物，包括空间受阻的2,2'-二取代-1,1'-联萘基。使用该[2 + 2 + 2]共环化作为关键步骤，可以实现天然芳基萘木脂素，黄豆苷元C，黄豆苷元E和脱氢脱氧鬼臼毒素的总合成。
• Studies on the constituents of the seeds of Hernandia ovigera L. VIII. Syntheses of (.+-.)-desoxypodophyllotoxin and (.+-.)-.BETA.-peltatin-A methyl ether.
  作者：Tatsuhiko KASHIMA、Mariko TANOGUCHI、Masao ARIMOTO、Hideo YAMAGUCHI

  DOI：10.1248/cpb.39.192

  日期：——

  (±)-Desoxypodophyllotoxin (2), a chief component of the seeds of Hernandia ovigera L., and (±)-β-peltatin-A methyl ether (3), an analogous phenyltetralin lignan, which have 2, 3-trans, 3, 4-cis configuration were synthesized according to the method developed for the synthesis of hernandin (1). The syntheses were pursued using the corresponding 4-phenyl-1, 2-dihydronaphthalene lactones (9 and 10) followed by cleavage of the lactone moiety to give the unsaturated hydroxy acids (11 and 12). Subsequent hydrogenation and ring closure by means of p-toluenesulfonic acid afforded both 2, 3-trans, 3, 4-cis and 2, 3-cis, 3, 4-cis ligans (2 and 13 or 3 and 14), which were isolated by preparative thin layer chromatography.

  (±)-去氧鬼臼毒素(2)是Hernandia ovigera L.种子中的主要成分，以及结构类似的苯基四氢萘木脂素(±)-β-peltatin-A甲基醚(3)，它们具有2,3-反式，3,4-顺式构型，根据合成Hernandin(1)的方法进行了合成。合成过程采用了相应的4-苯基-1,2-二氢萘内酯(9和10)，随后裂解内酯部分得到不饱和的羟基酸(11和12)。接下来的氢化和环化步骤使用对甲苯磺酸，得到了2,3-反式，3,4-顺式和2,3-顺式，3,4-顺式的木脂素(2和13或者3和14)，这些产物通过制备薄层色谱法进行了分离。
• A new route to 1-phenylnaphthalenes by cycloaddition: a simple and selective synthesis of some naphthalene lignan lactones
  作者：Seiichi Takano、Shizuo Otaki、Kunio Ogasawara

  DOI：10.1016/s0040-4039(00)98577-0

  日期：1985.1

  2-(2-Dithianyl)benzhydrols ( a-c) undergo facile cycloaddition reaction with maleic anhydride under thermal conditions to give 1-phenyl-naphthalenes ( a-c) in one step. The naphthalenes ( a-c) have been converted into the naphthalene lignan lactones, ( a-c) and ( a-c).

  在热条件下，将2-（2-二噻吩基）苯甲醇（ac）与马来酸酐进行简便的环加成反应，一步即可得到1-苯基-萘（ac）。萘（ac）已转化为萘木脂素内酯（ac）和（ac）。
• Stereoselective reactions. VIII. Stereochemical requirement for the benzylic oxidation of lignan lactone. A highly selective synthesis of the antitumor lignan lactone steganacin by the oxidation of stegane.
  作者：TSUNEO ISHIGURO、HIDEMICHI MIZUGUCHI、KIYOSHI TOMIOKA、KENJI KOGA

  DOI：10.1248/cpb.33.609

  日期：——

  A highly efficient synthesis of the antitumor steganin lignan steganacin (1) was accomplished. Bromination of stegane (7) with N-bromosuccinimide followed by treatment with aqueous tetrahydrofuran afforded steganol (3) in 85% yield. Acetylation of 3 gave 1 in 72% yield. Stegane (7) was also oxidized with 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone in AcOH to give 1 directly in 10% yield. Stereochemical requirements for the benzylic oxidation of dibenzocyclooctadiene lignan lactones are discussed.

  我们完成了抗肿瘤甜菜苷木质素甜菜苷（1）的高效合成。用 N-溴代丁二酰亚胺溴化 stegane (7)，然后用四氢呋喃水溶液处理，可得到 steganol (3)，收率为 85%。对 3 进行乙酰化后得到 1，收率为 72%。Stegane (7) 也在 AcOH 中与 2，3-二氯-5，6-二氰基-1，4-苯醌发生氧化反应，直接得到 1，收率为 10%。讨论了二苯并环辛二烯木质素内酯苄基氧化的立体化学要求。