dimethyl 2-[(2R,3S,12bS)-3-ethyl-1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a]quinolizin-2-yl]propanedioate | 18802-06-7

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 柯楠因类生物碱
• 英文名称: dimethyl 2-[(2R,3S,12bS)-3-ethyl-1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a]quinolizin-2-yl]propanedioate
• CAS: 18802-06-7；25921-27-1；61217-00-3；76376-53-9；130323-13-6
• 化学式: C₂₂H₂₈N₂O₄
• 分子量: 384.475
• InChiKey: OBRZTMWKJJSCFP-QBIMZIAESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  71.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl 2-[(2R,3S,12bS)-3-ethyl-1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a]quinolizin-2-yl]propanedioate 在 盐酸 、 二异丁基氢化铝 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 72.0h， 生成 (+/-)-hirsutine
  参考文献：
  名称：

  （±）-hirsutine和相关Corynanthé生物碱的立体选择性全合成

  摘要：

  在完全立体选择的序列中，已经通过新型的环戊二酮二聚体合成了二氢次磺基鸟嘌呤糖苷配基的类似物，并将其转化为四环吲哚生物碱。

  DOI：

  10.1039/c39840000847
• 作为产物：
  描述：

  3-Ethyl-1,4,6,7,12,12b-hexahydroindolo[2,3-a]quinolizine-4-carbonitrile 在 platinum(IV) oxide silver tetrafluoroborate 、 氢气 、 sodium hydride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 17.0h， 生成 dimethyl 2-[(2R,3S,12bS)-3-ethyl-1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a]quinolizin-2-yl]propanedioate
  参考文献：
  名称：

  Short synthesis of (±)-hirsutine: Direct addition of dimethyl malonate anion to a 1,4-conjugate iminium salt of appropriate 3-ethylindolo[2,3-a]quinolizidine

  摘要：

  Direct addition of dimethyl malonate anion to a 1,4-conjugate iminium salt of 3-ethylindolo[2,3-a]quinolizidine 4a (regenerated from the corresponding alpha-aminonitrile 4b) afforded enamine 5. Catalytic hydrogenation of compound 5, led stereoselectively to compound 6 (pseudo), which is the highly desired intermediate for the preparation of several Corynanthe alkaloids, including (+/-)-hirsutine 7. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)00056-7

文献信息

• Total Synthesis of (±)-Hirsutine: Application of Phosphine-Catalyzed Imine–Allene [4 + 2] Annulation
  作者：Reymundo A. Villa、Qihai Xu、Ohyun Kwon

  DOI：10.1021/ol302077n

  日期：2012.9.7

  The total synthesis of the indole alkaloid hirsutine has been achieved, with a key step being the application of our phosphine-catalyzed [4 + 2] annulation of an imine with ethyl α-methylallenoate. From commercially available indole-2-carboxaldehyde, the target was synthesized in 14 steps and 6.7% overall yield.

  吲哚生物碱毛素的全合成已经实现，其中一个关键步骤是应用我们的膦催化 [4 + 2] 亚胺与 α-甲基烯丙酸乙酯的环化。从市售的 indole-2-carboxaldehyde 合成目标物，分 14 步，总产率为 6.7%。
• New approaches to Corynanthe alkaloids involving the conjugate addition of dialkyl malonates to unsaturated thiolactams:Synthesis of (±)-3-epi-dihydrocorynantheol
  作者：Domingo Gomez-Pardo、Didier Desmaële、Jean d'Angelo

  DOI：10.1016/s0040-4039(00)61004-3

  日期：1992.10

  Addition of dimethyl malonate to thiolactam 8 led to a mixture of Michael adducts 9 and 10 (6:1, respectively). Copound 9 has been converted in 4 steps into (±)-3-epi-dihydrocorynantheol 16.

  将丙二酸二甲酯加到硫代内酰胺8中得到迈克尔加合物9和10（分别为6∶1）的混合物。化合物9已分4步转化为（±）-3-表-二氢七氢萘酚16。
• Short syntheses of hirsutine and geissoschizine
  作者：Ernest Wenkert、Yashwant D. Vankar、Jhillu S. Yadav

  DOI：10.1021/ja00547a041

  日期：1980.12
• Steroeselective total synthesis of (±)-hirsutine and related Corynanthé alkaloids
  作者：Richard T. Brown、Martin F. Jones、Mark Wingfield

  DOI：10.1039/c39840000847

  日期：——

  In a completely stereoseletive sequence, an analogue of dihydrosecologanin aglucone has been synthesised via a novel cyclopentenedione dimmer and converted into tetracyclic indole alkaloids.

  在完全立体选择的序列中，已经通过新型的环戊二酮二聚体合成了二氢次磺基鸟嘌呤糖苷配基的类似物，并将其转化为四环吲哚生物碱。
• Short synthesis of (±)-hirsutine: Direct addition of dimethyl malonate anion to a 1,4-conjugate iminium salt of appropriate 3-ethylindolo[2,3-a]quinolizidine
  作者：Mauri Lounasmaa、Jari Miettinen、Pirjo Hanhinen、Reija Jokela

  DOI：10.1016/s0040-4039(97)00056-7

  日期：1997.2

  Direct addition of dimethyl malonate anion to a 1,4-conjugate iminium salt of 3-ethylindolo[2,3-a]quinolizidine 4a (regenerated from the corresponding alpha-aminonitrile 4b) afforded enamine 5. Catalytic hydrogenation of compound 5, led stereoselectively to compound 6 (pseudo), which is the highly desired intermediate for the preparation of several Corynanthe alkaloids, including (+/-)-hirsutine 7. (C) 1997 Elsevier Science Ltd.