(dl)-5-(3,4,5-trimethoxyphenyl)-8a,9-dihydrofuro[3′,4’:6,7]-naphtho[2,3-d][1,3]dioxol-6(8H)-one | 6258-32-8

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 木脂素内酯
• 英文名称: (dl)-5-(3,4,5-trimethoxyphenyl)-8a,9-dihydrofuro[3′,4’:6,7]-naphtho[2,3-d][1,3]dioxol-6(8H)-one
• 英文别名: (+/-)-2-Hydroxymethyl-6,7-methylenedioxy-4-(3',4',5'-trimethoxyphenyl)-1,2-dihydro-3-naphthoic acid lactone；(+/-)-γ-apopicropodophyllin；5-(3,4,5-trimethoxy-phenyl)-8a,9-dihydro-8H-furo[3',4':6,7]naphtho[2,3-d][1,3]dioxol-6-one；rac-γ-Apopicropodophyllin；γ-Apo-picropodophyllin；5-(3,4,5-trimethoxyphenyl)-8a,9-dihydro-8H-[2]benzofuro[6,5-f][1,3]benzodioxol-6-one
• CAS: 6258-32-8
• 化学式: C₂₂H₂₀O₇
• 分子量: 396.397
• InChiKey: RHQXIIWKHDCEMQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 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：

  (dl)-5-(3,4,5-trimethoxyphenyl)-8a,9-dihydrofuro[3′,4’:6,7]-naphtho[2,3-d][1,3]dioxol-6(8H)-one 在 氯化铵 、 magnesium 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 3.0h， 以51.2%的产率得到(-)-isodehydropodophyllotoxin
  参考文献：
  名称：

  合成与计算研究表明分子内苯乙烯基Diels-Alder反应的效用和二吨-butylhydroxytoluene辅助[1,3] -换档构建抗癌DL -Deoxypodophyllotoxin

  摘要：

  脱氧鬼臼毒素是一种次生代谢产物木脂素，具有强大的抗癌活性，并有可能作为已知抗癌药的前体，但由于天然来源的缺乏，其使用受到了限制。我们在这里报告了使用分子内苯乙烯基Diels-Alder反应策略在七个步骤中进行的总外消旋体脱氧鬼臼毒素的合成，该策略独特地适合于组装脱氧鬼臼毒素的核心。使用密度泛函理论分析一致的，极性的，和单重开壳层双自由基反应途径，它标识一致的低能量[4 + 2]狄尔斯-阿尔德途径随后更快的二吨-butylhydroxytoluene辅助[1,2 3]-正式氢位移。

  DOI：

  10.1021/acs.joc.7b02957
• 作为产物：
  描述：

  (Z)-4-(2-Bromo-4,5-methylenedioxybenzyl)-3-(3,4,5-trimethoxybenzylidene)dihydro-2(3H)-furanone 在 bis-triphenylphosphine-palladium(II) chloride potassium carbonate 、 三苯基膦 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 以75%的产率得到(dl)-5-(3,4,5-trimethoxyphenyl)-8a,9-dihydrofuro[3′,4’:6,7]-naphtho[2,3-d][1,3]dioxol-6(8H)-one
  参考文献：
  名称：

  Synthesis of podophyllotoxin derivatives by means of tributyltin hydride- or palladium-mediated cyclization of α-benzylidene-β-(o-bromobenzyl)-γ-lactones

  摘要：

  Synthesis of podophyllotoxin derivatives based on an aryl radical cyclization of alpha-benzylidene-beta-(o-bromobenzyl)-gamma-lactones 20 and 21 has been examined. Treatment of a mixture of the alcohols 18a and 18b (ca. 1:1), prepared from 6-bromopiperonal (10) in 7 steps, with methanesulfonyl chloride gave a ca. 3:1 mixture of the chlorides 19a and 19b, which was treated with DBU to give the (Z)- and (E)-alpha-benzylidene-gamma-lactones 20 and 21 in 64 and 22% yields, respectively. Thermolysis of the mixture of the sulfoxides 23a and 23b, prepared from 18a,b, afforded the E-isomer 21 as a major product. The Z-benzylidenelactone 20 when treated with Bu3SnH in the presence of AIBN gave the 6-endo-trig radical cyclization product, (+/-)-deoxyisopicropodophyllin (24), and the 5-exo-trig cyclization product 25 in 29 and 49% yields, respectively. The E-isomer 21, however, gave only the 5-exo cyclization product 25. On the other hand, treatment of 20 with PdCl2(PPh3)3 gave (+/-)-gamma-apopicropodophyllin (29) in 75% yield. Similar treatment of 21 afforded no cyclization product, but, in the presence of sodium formate (H- source), gave the 5-exo cyclization product 25 in 84% yield.

  DOI：

  10.1016/s0040-4020(01)85735-5

文献信息

• 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。
• Ishibashi, Hiroyuki; Ito, Katsuhiro; Tabuchi, Masayo, Heterocycles, 1991, vol. 32, # 7, p. 1279 - 1282
  作者：Ishibashi, Hiroyuki、Ito, Katsuhiro、Tabuchi, Masayo、Ikeda, Masazumi

  DOI：——

  日期：——
• 80. The constituents of natural phenolic resins. Part IV. Synthesis of dehydroanhydropicropodophyllin
  作者：Robert D. Haworth、Thomas Richardson

  DOI：10.1039/jr9360000348

  日期：——
• Components of Podophyllin. IX. The Structure of the Apopicropodophyllins^1,2
  作者：Anthony W. Schrecker、Jonathan L. Hartwell

  DOI：10.1021/ja01142a037

  日期：1952.11
• Components of Podophyllin. XII.¹ The Configuration of Podophyllotoxin
  作者：Anthony W. Schrecker、Jonathan L. Hartwell

  DOI：10.1021/ja01119a040

  日期：1953.12