11-(Dimethylamino)-2-(methoxycarbonyl)-9H-imidazo<4',5':3,4>pyrido<2,3-b>indole | 169902-92-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 11-(Dimethylamino)-2-(methoxycarbonyl)-9H-imidazo<4',5':3,4>pyrido<2,3-b>indole
• 英文别名: Methyl 4-(dimethylamino)-3,5,8,10-tetrazatetracyclo[7.7.0.02,6.011,16]hexadeca-1,3,6,8,11,13,15-heptaene-7-carboxylate
• CAS: 169902-92-5
• 化学式: C₁₆H₁₅N₅O₂
• 分子量: 309.327
• InChiKey: NOWAHJXDUOGITQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  86.9
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  11-(Dimethylamino)-2-(methoxycarbonyl)-9H-imidazo<4',5':3,4>pyrido<2,3-b>indole 在 盐酸 、 叔丁基锂 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 3.0h， 生成 Grossularine-1
  参考文献：
  名称：

  Total synthesis of grossularines-1 and -2

  摘要：

  The first total syntheses of grossularines-1 (1a) and -2 (1b) have been completed. The cross-coupling reaction between ethyl 3-iodoindole-2-carboxylate (6) and the directed metalation-derived imidazole 9b gave the ethyl 3-(5-imidazolyl)indole-2-carboxylate 11b. Hydrolysis of the ester group of 11b, followed by Curtius rearrangement, yielded the 2-isocyanatoindole 13b. The thermal electrocyclic reaction of 13b was carried out to provide the desired tetracyclic pyrido[2,3-b]indole ring system 14b, which was converted into the triflate 15b. The three-component cross-coupling reaction of the triflate 15b, carbon monoxide, and p-(OMOM)phenylboronic acid (17) followed by hydrolysis gave grossularine-2 (1b) in low yield. In addition, the palladium-catalyzed carbonylation of the triflate 15b afforded the N-deprotected methyl ester 19a or the methyl ester 19b depending on the amounts of triethylamine used. Compound 19a was treated with either p-(OMOM)phenyllithium or 3-(N-TIPS)indolyllithium to obtain grossularine-2 (1b) and grossularine-1 (1a) (37%), respectively. By contrast, when 19b was treated with the same aryllithium reagents, grossularine-2 (1b) (51%) and grossularine-1 (1a) (63%) were produced, respectively.

  DOI：

  10.1021/jo00123a028
• 作为产物：
  描述：

  3-碘-1H-吲哚-2-甲酸乙酯 在 palladium diacetate 、 Pd(PPh3) 吡啶 、 1,1'-双(二苯基膦)二茂铁 、 二苯基磷酸 、 sodium carbonate 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 邻二氯苯 、 苯 为溶剂， 反应 25.58h， 生成 11-(Dimethylamino)-2-(methoxycarbonyl)-9H-imidazo<4',5':3,4>pyrido<2,3-b>indole
  参考文献：
  名称：

  Total synthesis of grossularines-1 and -2

  摘要：

  The first total syntheses of grossularines-1 (1a) and -2 (1b) have been completed. The cross-coupling reaction between ethyl 3-iodoindole-2-carboxylate (6) and the directed metalation-derived imidazole 9b gave the ethyl 3-(5-imidazolyl)indole-2-carboxylate 11b. Hydrolysis of the ester group of 11b, followed by Curtius rearrangement, yielded the 2-isocyanatoindole 13b. The thermal electrocyclic reaction of 13b was carried out to provide the desired tetracyclic pyrido[2,3-b]indole ring system 14b, which was converted into the triflate 15b. The three-component cross-coupling reaction of the triflate 15b, carbon monoxide, and p-(OMOM)phenylboronic acid (17) followed by hydrolysis gave grossularine-2 (1b) in low yield. In addition, the palladium-catalyzed carbonylation of the triflate 15b afforded the N-deprotected methyl ester 19a or the methyl ester 19b depending on the amounts of triethylamine used. Compound 19a was treated with either p-(OMOM)phenyllithium or 3-(N-TIPS)indolyllithium to obtain grossularine-2 (1b) and grossularine-1 (1a) (37%), respectively. By contrast, when 19b was treated with the same aryllithium reagents, grossularine-2 (1b) (51%) and grossularine-1 (1a) (63%) were produced, respectively.

  DOI：

  10.1021/jo00123a028

文献信息

• Total synthesis of grossularines-1 and -2
  作者：Tominari Choshi、Shiho Yamada、Eiichi Sugino、Takeshi Kuwada、Satoshi Hibino

  DOI：10.1021/jo00123a028

  日期：1995.9

  The first total syntheses of grossularines-1 (1a) and -2 (1b) have been completed. The cross-coupling reaction between ethyl 3-iodoindole-2-carboxylate (6) and the directed metalation-derived imidazole 9b gave the ethyl 3-(5-imidazolyl)indole-2-carboxylate 11b. Hydrolysis of the ester group of 11b, followed by Curtius rearrangement, yielded the 2-isocyanatoindole 13b. The thermal electrocyclic reaction of 13b was carried out to provide the desired tetracyclic pyrido[2,3-b]indole ring system 14b, which was converted into the triflate 15b. The three-component cross-coupling reaction of the triflate 15b, carbon monoxide, and p-(OMOM)phenylboronic acid (17) followed by hydrolysis gave grossularine-2 (1b) in low yield. In addition, the palladium-catalyzed carbonylation of the triflate 15b afforded the N-deprotected methyl ester 19a or the methyl ester 19b depending on the amounts of triethylamine used. Compound 19a was treated with either p-(OMOM)phenyllithium or 3-(N-TIPS)indolyllithium to obtain grossularine-2 (1b) and grossularine-1 (1a) (37%), respectively. By contrast, when 19b was treated with the same aryllithium reagents, grossularine-2 (1b) (51%) and grossularine-1 (1a) (63%) were produced, respectively.