(+)-(2S,3aR,8aS)-3a-Allyl-1,2-bis(methoxycarbonyl)-8-(phenylsulfonyl)-1,2,3,3a,8,8a-hexahydropyrrolo<2,3-b>indole | 157989-22-5

• 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: (+)-(2S,3aR,8aS)-3a-Allyl-1,2-bis(methoxycarbonyl)-8-(phenylsulfonyl)-1,2,3,3a,8,8a-hexahydropyrrolo<2,3-b>indole
• 英文别名: dimethyl (2S,3aS,8bR)-4-(benzenesulfonyl)-8b-prop-2-enyl-2,3a-dihydro-1H-pyrrolo[2,3-b]indole-2,3-dicarboxylate
• CAS: 157989-22-5
• 化学式: C₂₃H₂₄N₂O₆S
• 分子量: 456.519
• InChiKey: CEXFEIWQCNJDFJ-IEIRFRATSA-N

物化性质

• 沸点：
  576.8±60.0 °C(predicted)
• 密度：
  1.337±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (+)-(2S,3aR,8aS)-3a-Allyl-1,2-bis(methoxycarbonyl)-8-(phenylsulfonyl)-1,2,3,3a,8,8a-hexahydropyrrolo<2,3-b>indole 在 四氧化锇 氢氧化钾 、 sodium periodate 、 正丁基锂 、 1-oxa-2-oxo-3-thiaindolizinium chloride 、 sodium cyanoborohydride 、 叔丁基硫醇 、 溶剂黄146 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 36.25h， 生成 (+)-(3aR,8aS)-1-Methyl-3a-(3-methyl-2-buten-1-yl)-8-(phenylsulfonyl)-1,2,3,3a,8,8a-hexahydropyrrolo<2,3-b>indole
  参考文献：
  名称：

  Chemistry of Cyclic Tautomers of Tryptophan: Formation of a Quaternary Center at C3a and Total Synthesis of the Marine Alkaloid (+)-ent-Debromoflustramine B

  摘要：

  A diastereoselective synthesis of the unnatural (+)-enantiomer of the marine alkaloid (-)-debromoflustramine B (1) from a cyclic tautomer (9) of L-tryptophan is described. The optical rotation of the synthetic 1 is opposite to that of the natural material enabling the configuration of the natural product to be established as 3aS,8aR. As natural flustramine B has been converted to (-)-debromoflustramine B its absolute configuration may also be set as 3aS,8aR. The synthetic scheme involves radical bromination of 9 at C3a followed by allylation, at C3a, with allyltributyltin to give 21. The allyl group is then converted to the C3a prenyl derivative 23 by oxidative cleavage and Wittig reaction. The remainder of the synthesis involves removal of the now extraneous carbomethoxy group from C2 and selective removal of the two nitrogen protecting groups and alkylation of the resulting amines. Oxidation of 9 with eerie ammonium nitrate to give mixtures of the C3a nitrato- and hydroxy-derivatives 18 and 19 is also described.

  DOI：

  10.1021/jo00098a011
• 作为产物：
  描述：

  α-甲基色氨酸前体 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 作用下， 以 四氯化碳 、 苯 为溶剂， 反应 18.5h， 生成 (+)-(2S,3aR,8aS)-3a-Allyl-1,2-bis(methoxycarbonyl)-8-(phenylsulfonyl)-1,2,3,3a,8,8a-hexahydropyrrolo<2,3-b>indole
  参考文献：
  名称：

  Chemistry of Cyclic Tautomers of Tryptophan: Formation of a Quaternary Center at C3a and Total Synthesis of the Marine Alkaloid (+)-ent-Debromoflustramine B

  摘要：

  A diastereoselective synthesis of the unnatural (+)-enantiomer of the marine alkaloid (-)-debromoflustramine B (1) from a cyclic tautomer (9) of L-tryptophan is described. The optical rotation of the synthetic 1 is opposite to that of the natural material enabling the configuration of the natural product to be established as 3aS,8aR. As natural flustramine B has been converted to (-)-debromoflustramine B its absolute configuration may also be set as 3aS,8aR. The synthetic scheme involves radical bromination of 9 at C3a followed by allylation, at C3a, with allyltributyltin to give 21. The allyl group is then converted to the C3a prenyl derivative 23 by oxidative cleavage and Wittig reaction. The remainder of the synthesis involves removal of the now extraneous carbomethoxy group from C2 and selective removal of the two nitrogen protecting groups and alkylation of the resulting amines. Oxidation of 9 with eerie ammonium nitrate to give mixtures of the C3a nitrato- and hydroxy-derivatives 18 and 19 is also described.

  DOI：

  10.1021/jo00098a011

文献信息

• The chemistry of cyclic tautomers of tryptophan: Total synthesis of (+)-(ent)-pseudophrynaminol
  作者：David Crich、Anna B. Pavlovic、Raghu Samy

  DOI：10.1016/0040-4020(95)00307-t

  日期：1995.6

  A diastereoselective synthesis of the unnatural (+)-enantiomer of the hexahydropyrroloindole alkaloid (-)-pseudophrynaminol (3), isolated from the skin of the Australian frog Pseudophryne coriacea, from a cyclic tautomer (1) of L-tryptophan, is described, The CD spectrum of the synthetic 3 is opposite in sign to that of the natural material enabling the configuration of the natural product to be established as 3aS,8aR.