Development of simple methods for the preparation of heterocycle-fused quinones and their application to the synthesis of natural products

杂环稠合醌的简单制备方法的开发及其在天然产物合成中的应用

• 批准号: 10650852
• 负责人: KOBAYASHI Kazuhiro
• 金额: $ 2.18万
• 依托单位: Tottori University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10650852/
• 关键词: quinones; indoles; thiophenes; pyrans; furans; enamines; imines; conjugate addition; イソキノリン; アントラキノン; ピロール

1H-Naphtho[2, 3-c]pyran-5, 10-dione derivatives, including a natural product (pentalongin), were generally synthesized in one-pot using a tandem conjugate addition-cyclization sequence between 2-(1-hydroxylkyl)-1, 4-naphthoquinones and enamines (or imines). The utility of this method was demonstrated in the synthesis of pyranonaphthoquinone antibiotics, (±)-eleutherin and (±)-isoeleutherin.The reaction of 2-hydroxy-1, 4-naphthoquinones with 0-fluoronitrobenzenes in the presence of KィイD22ィエD2COィイD23ィエD2 in DMSO gave 2-hydroxy-3-(2-nitroaryl)-1, 4-naphthoquinones in fair yields, which in turn were transformed into the corresponding 11H-benzo[a]carbazole-5, 6-dione and 5H-benzo[b]carbzole^6, 11-dione derivatives in good yields by catalytic hydrogenation over PtOィイD22ィエD2 in AcOEt, followed by exposure to air and then heating at reflux temperature.Naphtho[2, 3-b]thiophene-4, 9-quinones were generally synthesized in one-pot using a tandem conjugate addition-cyclization sequence between 2-[2 … More -(ethoxycarbonyl)-ethyl]thio-1, 4-naphthoquinone and enamines, derived from cyclic and acyclic ketones.The reaction of 4-hydroxy-2H-pyran-2-one derivatives with a range of alkenes or phenylacetylene in acetonitrile containing cerium(IV) ammonium nitrate (CAN) afforded the corresponding furo[3, 2-c]pyranone and/or furo[2, 3-b]pyranone derivatives. Similar treatment of 4-hydroxy-1-methylquinolin-2(1H)-one with alkenes or phenylacetylene in the presence of CAN gave furo[3, 2-c]quinolin-4(5H)-one derivatives.2-Acetyl-1, 4-naphthoquinone was treated with pyrrolidine (or morpholine) enamines, derived from cyclic and acyclic ketones, in DMF at room temperature for 24-72 h to afford 3, 4-distributed 1-pyrrolidino(or morpholino)-9, 10-anthraquinones. On the other hand, when the treatment of 2-acetyl-1, 4-naphthoquinone with enamines for 2 min was followed by addition of water and heating at 100℃ for 2 h, the corresponding 1-hydroxy-9, 10-naphthoquinone derivatives were obtained.The reaction of 1, 3-dimethylpyrimidine-2, 4, 6(1H, 3H, 5H)-trione with various alkenes or terminal alkynes in the presence of cerium(IV) ammonium nitrate (CAN) afforded the corresponding 5, 6-dihydrofuro[2, 3-d]pyrimidine-2, 4(1H, 3H)-diones or furo[2, 3-d]pyrimidine-2, 4(1H, 3H)-diones in moderate to good yields. Less

通常，使用串联偶联物的添加序列在2-（1-Hydroxylkyl）之间合成1H-萘[2，3-C] pyran-5，10二酮衍生物，包括天然产物（pentalOngin），在一锅中合成。该方法的实用性在合成吡anaNaphophoone抗生素，（±） - 素蛋白和（±） - 异素蛋白。2-羟基-1、4-萘喹酮与0-氟甲硝基苯甲酸的反应在k-d22，co-d22，d23，d2 in d2，d2 in 2-hydroxy-3-(2-nitroaryl)-1, 4-naphthoquinones in fair yields, which in turn were transformed into the corresponding 11H-benzo[a]carbazole-5, 6-dione and 5H-benzo[b]carbzole^6, 11-dione derivatives in good yields by catalytic hydrogenation over PtOi D22 in AcOEt, followed by exposure to air and然后在反射液温度下加热[2，3-b]噻吩-4，9-喹酮，通常使用串联共轭加成序列序列在2- [2…更多 - （乙氧基核） - 乙基）-1-甲基]硫酮和4-萘酮的反应中合成，并在2- [2…more-（ethoxycarbonyl）之间合成。 4-羟基-2H-2H-Pyran-2-衍生物具有一系列烯烃或苯乙烯中的乙腈中，含有葡萄岩（IV）硝酸铵（CAN）提供了相应的Furo [3，2-C]吡喃酮和/或furo [2，3-b] Pyranone pyranone衍生物。在存在下与烷烃或苯乙烯的4-羟基-1-甲基喹啉-2（1H）的类似处理可以给出[3，2-c] quinolin-4（5h） - 一种衍生物。2-乙酰基-1，另一方面是2分钟的4-奈夫蛋白，随后是2分钟的4-奈夫，在2-乙基蛋白酶的范围内进行2分钟4-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-n-Naphth，水和加热在100°，持续2小时，获得了相应的1-羟基-9，10-萘醌衍生物。在存在（IV）硝酸铵（CAN）的情况下，1、3-二甲基二酰胺-2、4、6（1H，3H，5H） - 环与各种烷烃或末端炔的反应与相应的5，6-二尿[2，3-D] Pyrimidine-2，4（1H）的反应。较少的

项目成果

小林和裕: "Syntheses of 1-amino- and 1-hydroxy-9,10-anthraquinone derivatives based on reaction sequences between 2-acetyl-1,4-naphthoquinone and enamines"Tetrahedron Letters. 41・(印刷中). (2000)

Kazuhiro Kobayashi：“基于 2-乙酰基-1,4-萘醌和烯胺之间的反应序列合成 1-氨基-和 1-羟基-9,10-蒽醌衍生物”Tetrahedron Letters 41·（出版中）。 ）

小林 和裕: "One-step synthesis of furo[2,3-d]pyrimidine-2,4(1H,3H)-diones using the CAN-mediated furan ring formation"Synthetic Communications. 30・(印刷中). (2000)

Kazuhiro Kobayashi：“利用 CAN 介导的呋喃环形成一步合成呋喃[2,3-d]嘧啶-2,4(1H,3H)-二酮”Synthetic Communications 30·（出版中）。 ）

Kazuhiro Kobayashi: "CAN-mediated formation of furopyranones and furoquinolinones"Heterocycles. 51. 2881-2892 (1999)

Kazuhiro Kobayashi：“CAN 介导的呋喃吡喃酮和呋喃喹啉酮的形成”杂环。

小林和裕: "CAN-mediated formation of furopyranones and furoquinolinones"Heterocycles. 51. 2881-2892 (1999)

Kazuhiro Kobayashi：“CAN 介导的呋喃吡喃酮和呋喃喹啉酮的形成”杂环。 51. 2881-2892 (1999)

Kazuhiro Kobayashi: "Syntheses of 1-amino- and 1-hydroxy-9, 10-anthraquinone derivatives based on reaction sequences between 2-acetyl-1, 4-naphthoquinone and enamines"Tetrahedron Letters. 41, (in press). (2000)

Kazuhiro Kobayashi：“基于 2-乙酰基-1, 4-萘醌和烯胺之间的反应序列合成 1-氨基-和 1-羟基-9, 10-蒽醌衍生物”Tetrahedron Letters。