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

1H-萘并[2，3-c]吡喃-5，10-二酮类化合物，包括一种天然产物，通常是通过2-(1-羟基基)-1，4-萘醌和烯胺(或亚胺)之间的串联共轭加成-环化反应在一锅中合成的。2-羟基-1，4-萘醌与邻氟硝基苯在二甲基亚砜存在下，在KィイD22ィエD2COィイD23ィエD2存在下反应生成2-羟基-3-(2-硝基芳基)-1，4-萘醌类化合物，再转化为相应的11H-苯并[a]咔唑-5，6-二酮和5H-苯并[b]咔唑。11-二酮类化合物在ィイD22ィエD2催化剂上催化加氢，然后暴露在空气中，然后在回流温度下加热，产率很高。通常采用2-[2…]之间的串联共轭加成-环化序列在一锅中合成并[2，3-b]噻吩并-4，9-苯二酮4-羟基-2H-吡喃-2-酮衍生物与一系列烯烃或苯乙炔在含硝酸铈的乙腈中反应得到相应的呋喃并[3，2-c]吡喃酮和/或呋喃并[2，3-b]吡喃酮衍生物。4-羟基-1-甲基喹啉-2(1H)-酮与烯烃或苯乙炔在CaN存在下反应得到呋喃[3，2-c]喹啉-4(5H)-酮衍生物2-乙酰基-1，4-萘醌与环酮和非环酮衍生的吡咯烷(或吗啉)烯胺在DMF中于室温下反应24-72 h，得到3，4-分布的1-吡咯烷基(或吗啉)-9，10-蒽醌类化合物。另一方面，2-乙酰基-1，4-萘醌与烯胺反应2min，然后加水，在100℃下加热2 h，得到相应的1-羟基-9，10-萘醌衍生物。1，3-二甲基嘧啶-2，4，6(1H，~3H，5H)-三酮与不同的烯烃或末端炔烃在硝酸铈存在下反应得到相应的5，6-二氢呋喃并[2，3-d]嘧啶-2，4(1H，3H)-二酮或呋喃[2，3-d]3-D]嘧啶-2，4(1H，3H)-二酮，产率中等到较好。较少

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）。 ）

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: "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。

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。