(S)-5,8-dimethoxy-3-methyl-3,4-dihydro-1H-2-benzopyran | 154230-67-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: (S)-5,8-dimethoxy-3-methyl-3,4-dihydro-1H-2-benzopyran
• 英文别名: (+)-(S)-5,8-dimethoxy-3-methyl-3,4-dihydro-1H-benzo[c]pyran；5,8-Dimethoxy-3-methyl-1H-isochroman；(3S)-5,8-dimethoxy-3-methyl-3,4-dihydro-1H-isochromene
• CAS: 154230-67-8
• 化学式: C₁₂H₁₆O₃
• 分子量: 208.257
• InChiKey: WBVSORXDJBJEQE-QMMMGPOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-5,8-dimethoxy-3-methyl-3,4-dihydro-1H-2-benzopyran 在 ammonium cerium (IV) nitrate 作用下， 以 水 、 乙腈 为溶剂， 以92%的产率得到(+)-(S)-3-methyl-3,4-dihydro-1H-2-benzopyran-5,8-dione
  参考文献：
  名称：

  用于对映选择性合成 (+)-Nanomycin A 甲酯、(+)-Eleutherin、(+)-Allo-Eleutherin 和 (+)-Thysanone 脱氧类似物的分子内和分子间 Oxa-Pictet-Spengler 环化策略

  摘要：

  吡喃萘醌类抗生素 (+)-纳米霉素 A 甲酯、(+)-eleutherin、(+)-allo-eleutherin 和 (+)-thysanone 的脱氧类似物的对映选择性合成以良好的总收率实现，具有高对映选择性和非对映选择性常见的中间体（R）-3-（2,5-二甲氧基苯基）丙烷-1,2-二醇。首次开发了 6-芳基-1,3-二氧戊环的分子内氧杂-Pictet-Spengler 环化，并将其用于 (+)-脱氧纳米霉素 A 甲酯的对映选择性合成，而分子间氧杂-Pictet-Spengler 环化策略应用于 (+)-eleutherin、(+)-allo-eleutherin 和 (+)-thysanone 脱氧类似物的对映选择性合成。

  DOI：

  10.1002/ejoc.201000476
• 作为产物：
  描述：

  (E)-1,4-dimethoxy-2-(2-nitroprop-1-en-1-yl)benzene 在 1-[([1,3,2]dioxaborolan-2-yloxy)-diphenyl-methyl]-2-methylpropylamine 、 dimethyl sulfide borane 、 铁粉 、 溶剂黄146 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 9.5h， 生成 (S)-5,8-dimethoxy-3-methyl-3,4-dihydro-1H-2-benzopyran
  参考文献：
  名称：

  Enantioselective Formal Synthesis of the Cytotoxic Topoisomerase II Inhibitor Deoxythysanone, Catalyzed by Chiral Spiroborate Ester

  摘要：

  Bioactive pyranonaphthoquinone analogs, (1R,3S)-deoxythysanone, (1R,3S)-thysanone, and (1R,3S)-demethoxythysanone can be efficiently synthesized from a common intermediate product, (S)-3-methyl-3,4-dihydro-1H-isochromene-5,8-dione. We have developed a short synthetic route to pyranonaphthoquinone antibiotics, which involves enantioselective reduction of homobenzylic ketone in the presence of a chiral spiroborate catalyst with 87% enantiomeric excess as the key step. The subsequent oxa-Pectet-Spengler reaction, followed by oxidative demethylation, afforded deoxythysanone.

  DOI：

  10.1134/s1070428020040181

文献信息

• Intra- and Intermolecular Oxa-Pictet-Spengler Cyclization Strategy for the ­Enantioselective Synthesis of Deoxy Analogues of (+)-Nanomycin A Methyl Ester, (+)-Eleutherin, (+)-Allo-Eleutherin, and (+)-Thysanone
  作者：Rajiv T. Sawant、Satish G. Jadhav、Suresh B. Waghmode

  DOI：10.1002/ejoc.201000476

  日期：——

  Enantioselective synthesis of deoxy analogues of pyranonaphthoquinone antibiotics (+)-nanomycin A methyl ester, (+)-eleutherin, (+)-allo-eleutherin, and (+)-thysanone was achieved in good overall yield with high enantio- and diastereoselectivity from the common intermediate (R)-3-(2,5-dimethoxyphenyl)propane-1,2-diol. The intramolecular oxa-Pictet–Spengler cyclization of 6-aryl-1,3-dioxolone was developed

  吡喃萘醌类抗生素 (+)-纳米霉素 A 甲酯、(+)-eleutherin、(+)-allo-eleutherin 和 (+)-thysanone 的脱氧类似物的对映选择性合成以良好的总收率实现，具有高对映选择性和非对映选择性常见的中间体（R）-3-（2,5-二甲氧基苯基）丙烷-1,2-二醇。首次开发了 6-芳基-1,3-二氧戊环的分子内氧杂-Pictet-Spengler 环化，并将其用于 (+)-脱氧纳米霉素 A 甲酯的对映选择性合成，而分子间氧杂-Pictet-Spengler 环化策略应用于 (+)-eleutherin、(+)-allo-eleutherin 和 (+)-thysanone 脱氧类似物的对映选择性合成。
• DDQ-induced and stereoselective functionalization at heterosubstituted benzylic positions by carbon nucleophiles
  作者：Xu Yao-Chang、Caroline Roy、Elaine Lebeau

  DOI：10.1016/s0040-4039(00)61387-4

  日期：1993.12
• DDQ-Induced, Anomeric Specific, and Diastereoselective Benzylic Glycosidation: A Novel Approach to Heterocyclic Anthracycline Antibiotics
  作者：Yao-Chang Xu、Elaine Lebeau、Giorgio Attardo、Peter L. Myers、John W. Gillard

  DOI：10.1021/jo00096a032

  日期：1994.8

  A novel and efficient method for the oxidative glycosidation at the heterosubstituted benzylic positions with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) is described. The reaction is stereospecific with 3-substituted isochromans and isothiochroman, as well as diastereoselective with non-3-substituted isochromans. The glycosidation with a mixture of alpha- and beta-anomeric free sugars gives alpha-glycosides with absolute stereochemical control on the anomeric center. The synthetic utility of this novel methodology is demonstrated by a short, efficient, and stereoselective total synthesis of heteroanthracycline antitumor reagents.
• Enantioselective Formal Synthesis of the Cytotoxic Topoisomerase II Inhibitor Deoxythysanone, Catalyzed by Chiral Spiroborate Ester
  作者：M. U. Chopade、M. D. Nikalje、H. S. Patil、A. U. Chopade

  DOI：10.1134/s1070428020040181

  日期：2020.4

  Bioactive pyranonaphthoquinone analogs, (1R,3S)-deoxythysanone, (1R,3S)-thysanone, and (1R,3S)-demethoxythysanone can be efficiently synthesized from a common intermediate product, (S)-3-methyl-3,4-dihydro-1H-isochromene-5,8-dione. We have developed a short synthetic route to pyranonaphthoquinone antibiotics, which involves enantioselective reduction of homobenzylic ketone in the presence of a chiral spiroborate catalyst with 87% enantiomeric excess as the key step. The subsequent oxa-Pectet-Spengler reaction, followed by oxidative demethylation, afforded deoxythysanone.