1,2-Dimethoxycarbonyl-8-acetyl-1,2,3,3a,8,8a-hexahydropyrrolo<2,3-b>indole | 79465-85-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1,2-Dimethoxycarbonyl-8-acetyl-1,2,3,3a,8,8a-hexahydropyrrolo<2,3-b>indole
• 英文别名: L-(2β,3aα,8aα)-8-acetyl-1,2-dimethoxycarbonyl-1,2,3,3a,8,8a-hexahydropyrrolo<2,3-b>indole；dimethyl (2S,3aR,8aS)-8-acetyl-1,2,3,3a,8,8a-hexahydropyrrolo<2,3-b>indole-1,2-dicarboxylate；dimethyl (2S,3aR,8bR)-4-acetyl-1,2,3a,8b-tetrahydropyrrolo[2,3-b]indole-2,3-dicarboxylate
• CAS: 79465-85-3
• 化学式: C₁₆H₁₈N₂O₅
• 分子量: 318.329
• InChiKey: ZKMAGAPYZQZBHO-KWCYVHTRSA-N

物化性质

• 沸点：
  492.6±45.0 °C(Predicted)
• 密度：
  1.318±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  76.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,2-Dimethoxycarbonyl-8-acetyl-1,2,3,3a,8,8a-hexahydropyrrolo<2,3-b>indole 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 溶剂黄146 为溶剂， 生成 5-Cyano-N_b-methoxycarbonyl-N_a-acetyl-L-tryptophan methyl esterolo<2,3-b>indole
  参考文献：
  名称：

  Synthesis of 5-cyano-l-tryptophan

  摘要：

  The 5-bromo derivative 2 of the cyclic tautomer of N(b)-methoxycarbonyl-L-tryptophan methyl ester 1 undergoes reaction with CuCN in refluxing N-methylpyrrolidone (NMP) to give 5-cyano derivative 3a with some ring opened 5-cyano product 3b. Both 3a and 3b can be converted, in high yield, into free 5-cyano-L-tryptophan 4 with BBr3 under mild conditions.

  DOI：

  10.1016/s0040-4039(00)77665-9
• 作为产物：
  描述：

  N-(methoxycarbonyl)-L-tryptophan methyl ester 在 吡啶 、 磷酸 作用下， 生成 1,2-Dimethoxycarbonyl-8-acetyl-1,2,3,3a,8,8a-hexahydropyrrolo<2,3-b>indole
  参考文献：
  名称：

  Synthesis of 5-cyano-l-tryptophan

  摘要：

  The 5-bromo derivative 2 of the cyclic tautomer of N(b)-methoxycarbonyl-L-tryptophan methyl ester 1 undergoes reaction with CuCN in refluxing N-methylpyrrolidone (NMP) to give 5-cyano derivative 3a with some ring opened 5-cyano product 3b. Both 3a and 3b can be converted, in high yield, into free 5-cyano-L-tryptophan 4 with BBr3 under mild conditions.

  DOI：

  10.1016/s0040-4039(00)77665-9

文献信息

• Cyclic tautomers of tryptophans and tryptamines—4
  作者：Mikio Taniguchi、Tohru Hino

  DOI：10.1016/s0040-4020(01)92088-5

  日期：1981.1

  Nb-Methoxycarbonyltryptophan methyl ester (dl- and l-13) was cyclized to the corresponding rans cyclic tautomer (14) in excellent yield in various acids such as 85% phosphoric acid or trifluoroacetic acid. The cis cyclic tautomer (15) was formed as the less stable and kinetically controlled product and converted to the more stable trans isomer (14) under the reaction condition. The trans isomer (14)

  Ñ b -Methoxycarbonyltryptophan甲酯（DL-和1- 13）环化为相应的RANs环状互变异构体（14，在各种酸如85％的磷酸或三氟乙酸优良产率）。的顺式环互变异构体（15）形成为较不稳定的和动力学控制的产品，并转换为更稳定的反式异构体（14反应条件下）。用10％硫酸的甲醇溶液处理，将反式异构体（14）还原为13。其他色氨酸和色胺衍生物（6和19a）在相似的酸性介质中也被环化成相应的环状互变异构体。
• Total Synthesis of (+)-Elacomine and (?)-Isoelacomine, Two Hitherto Unnamed Oxindole Alkaloids fromElaeagnus commutata
  作者：Claudio Pellegrini、Michael Weber、Hans-J�rg Borschberg

  DOI：10.1002/hlca.19960790116

  日期：1996.2.7

  Racemic elacomine ((±)-2), a hemiterpene spiro oxindole alkaloid from Elaeagnus commutata, was synthesized in five steps from 6-methoxytryptamine (19) in 16% overall yield (Scheme 3). The final oxidative rearrangement of the corresponding β-carboline precursor (±)-21 furnished isoelacomine ((±)-22) as a by-product (6% overall yield). A more elaborate route that started from L-tryptophan furnished (+)-2

  外消旋可卡因（（±）-2）是一种从Elaeagnus commutata合成的半萜烯螺形羟吲哚生物碱，由6个甲氧基色胺（19）分五步合成，总收率为16％（方案3）。相应的β-咔啉前体（±）-21的最终氧化重排提供了副产物异丁香碱（（±）-22）（6％的总收率）。从L-色氨酸提供的（+）- 2和（-）- 22的光学纯度为76％（方案4）开始，这是一条更精细的路线，并确定了这些化合物的绝对构型。的根的生物碱含量的重新调查E. commutata 结果表明，可卡因和异可卡因均以外消旋形式自然存在。
• Synthesis of 5-Alkyl- and 5-Aryl-L-Tryptophan Analogues via Palladium-Catalyzed Cross-Coupling of an Iodinated Cyclic Tryptophan Tautomer
  作者：David E. Zembower、Matthew M. Ames

  DOI：10.1055/s-1994-25708

  日期：——

  Cyclic tryptophan tautomers have been shown to be useful intermediates in the preparation of optically pure tryptophans substituted in the benzenoid ring. We have utilized cyclic tautomer 2a for the preparation of L-tryptophan derivatives bearing 5-alkyl and 5-aryl functionalities. Treatment of 2a with 4 equivalents of iodine monochloride provided the 5-iodo species 3a in 81% yield. Cross-coupling of 3a with arylboronic acids or B-alkyl-9-borabicyclo[3.3.1]nonane derivatives, catalyzed by 3 mol% [bis(1,1′-diphenylphosphino)ferrocene]palladium(II) chloride, afforded the 5-aryl and 5-alkyl cyclic tryptophan tautomers 3b-g in 59-79% yields. The cyclic tautomers were easily decyclized and deprotected to give the corresponding 5-aryl- and 5-alkyl-L-tryptophans.

  环状色氨酸互变异构体已被证明是制备苯环取代的光学纯色氨酸的有用中间体。我们利用环状互变异构体2a来制备带有5-烷基和5-芳基官能团的L-色氨酸衍生物。用4当量的一氯化碘处理2a，得到5-碘物质3a，产率81%。 3a与芳基硼酸或B-烷基-9-硼双环[3.3.1]壬烷衍生物在3 mol%[双(1,1'-二苯基膦基)二茂铁]氯化钯(II)催化下交叉偶联，得到5 -芳基和5-烷基环状色氨酸互变异构体3b-g，产率为59-79%。环状互变异构体很容易脱环和脱保护，得到相应的5-芳基-和5-烷基-L-色氨酸。
• Taniguchi, Mikio; Anjiki, Tomiko; Nakagawa, Masako, Chemical and pharmaceutical bulletin, 1984, vol. 32, # 7, p. 2544 - 2554
  作者：Taniguchi, Mikio、Anjiki, Tomiko、Nakagawa, Masako、Hino, Tohru

  DOI：——

  日期：——
• Taniguchi, Mikio; Gonsho, Akinori; Nakagawa, Masako, Chemical and pharmaceutical bulletin, 1983, vol. 31, # 6, p. 1856 - 1865
  作者：Taniguchi, Mikio、Gonsho, Akinori、Nakagawa, Masako、Hino, Tohru

  DOI：——

  日期：——