(+/-)-Egenine | 6883-44-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢异喹啉
• 英文名称: (+/-)-Egenine
• 英文别名: (6S)-6-[(5R)-6-methyl-7,8-dihydro-5H-[1,3]dioxolo[4,5-g]isoquinolin-5-yl]-6,8-dihydrofuro[3,4-g][1,3]benzodioxol-8-ol
• CAS: 6883-44-9；11014-02-1；131614-66-9；131614-67-0；131681-55-5；131681-56-6
• 化学式: C₂₀H₁₉NO₆
• 分子量: 369.374
• InChiKey: YMHFBUOKLSWOQF-ZOVQDZKKSA-N

物化性质

• 沸点：
  511.3±50.0 °C(Predicted)
• 密度：
  1.478±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  27
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  69.6
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (+/-)-Egenine 在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 以73%的产率得到bicucullinediol
  参考文献：
  名称：

  Synthesis of the phthalide isoquinoline alkaloids (-)-egenine, (-)-corytensine, and (-)-bicuculline by asymmetric carbonyl addition of chiral dipole-stabilized organometallics

  摘要：

  The asymmetric addition of metalated [(methylenedioxy)isoquinolyl]oxazolines is 100% selective for the erythro (alpha-hydroxybenzyl)isoquinoline diastereomers, with 2:1 selectivity of the two possible erythro stereoisomers. Enrichment to 100% ee after removal of the auxiliary and conversion to (-)-bicuculline and (+)-bicuculline diol establish the absolute configuration of the major addition product. Inversion of the C-9 hydroxyl affords entry into the threo series as well. The asymmetric carbonyl addition was used to synthesize, for the first time, the phthalide-isoquinoline hemiacetals corytensine and egenine, confirming the previously assigned structures and absolute configurations, and establishing the identity of egenine with decumbensine and of corytensine with epi-alpha-decumbensine.

  DOI：

  10.1021/jo00004a041
• 作为产物：
  描述：

  5-甲酰基苯并[1,3]二恶茂-4-甲酸乙酯 在 lithium aluminium tetrahydride 、 草酰氯 、 二甲基亚砜 作用下， 生成 (+/-)-Egenine
  参考文献：
  名称：

  路易斯酸络合的杂原子碳负离子；α-羟基苄基四氢异喹啉生物碱的简便方法

  摘要：

  用仲丁基锂处理6,7-亚甲基二氧基-2-甲基四氢异喹啉的BF 3络合物（2），然后加入胡椒醛得到α-羟基苄基四氢异喹啉3a和3b，同时加入3,4-亚甲基二氧基邻苯二甲醛（4）得到生物碱（ ±）corytensine（5）和（±）egenine（6）以及同分异构的半缩醛7和8。

  DOI：

  10.1016/s0040-4039(00)79728-0

文献信息

• Short synthesis of noscapine, bicuculline, egenine, capnoidine, and corytensine alkaloids through the addition of 1-siloxy-isobenzofurans to imines
  作者：Maria Del Pilar C. Soriano、Nagula Shankaraiah、Leonardo Silva Santos

  DOI：10.1016/j.tetlet.2010.01.104

  日期：2010.3

  A concise diastereotioselective strategy for the synthesis of noscapine, bicuculiine, and egenine (1a-c), as well as capnoidine and corytensine (2a,b), was developed using diastereoselective addition of 1-siloxy-isobenzofurans 4a and 4b to immium ion 5 in a one-pot approach. The synthesis features the use of imine 13 obtained through Bischler-Napieralsky reaction from airline 11. The addition of ionic liquids as addictives in the reactions afforded erythro configuration in major adduct compounds. The synthetic route can also be applied in the total synthesis of promising tubulin binding agent EM105 (3). (C) 2010 Elseviet Ltd. All rights reserved.
• REIN, KATHLEEN S.;GAWLEY, ROBERT E., TETRAHEDRON LETT., 31,(1990) N6, C. 3711-3714
  作者：REIN, KATHLEEN S.、GAWLEY, ROBERT E.

  DOI：——

  日期：——
• REIN, KATHLEEN S.;GAWLEY, ROBERT E., J. ORG. CHEM., 56,(1991) N, C. 1564-1569
  作者：REIN, KATHLEEN S.、GAWLEY, ROBERT E.

  DOI：——

  日期：——
• Lewis acid complexed heteroatom carbanions; a convenient route to α-hydroxybenzyltetrahydroisoquinoline alkaloids
  作者：S.V. Kessar、Rahul Vohra、Nachhattar Pal Kaur

  DOI：10.1016/s0040-4039(00)79728-0

  日期：1991.7

  Treatment of the BF3 complex of 6,7-methylenedioxy-2-methyltetrahydroisoquinoline (2) with sec-butyllithium followed by addition of piperonal gave α -hydroxybenzyltetrahydroisoquinolines 3a and 3b, while addition of 3,4-methylenedioxyphthaldehyde (4) afforded alkaloids (±)corytensine (5) and (±) egenine (6) along with isomeric hemiacetals 7 and 8.

  用仲丁基锂处理6,7-亚甲基二氧基-2-甲基四氢异喹啉的BF 3络合物（2），然后加入胡椒醛得到α-羟基苄基四氢异喹啉3a和3b，同时加入3,4-亚甲基二氧基邻苯二甲醛（4）得到生物碱（ ±）corytensine（5）和（±）egenine（6）以及同分异构的半缩醛7和8。
• Synthesis of the phthalide isoquinoline alkaloids (-)-egenine, (-)-corytensine, and (-)-bicuculline by asymmetric carbonyl addition of chiral dipole-stabilized organometallics
  作者：Kathleen S. Rein、Robert E. Gawley

  DOI：10.1021/jo00004a041

  日期：1991.2

  The asymmetric addition of metalated [(methylenedioxy)isoquinolyl]oxazolines is 100% selective for the erythro (alpha-hydroxybenzyl)isoquinoline diastereomers, with 2:1 selectivity of the two possible erythro stereoisomers. Enrichment to 100% ee after removal of the auxiliary and conversion to (-)-bicuculline and (+)-bicuculline diol establish the absolute configuration of the major addition product. Inversion of the C-9 hydroxyl affords entry into the threo series as well. The asymmetric carbonyl addition was used to synthesize, for the first time, the phthalide-isoquinoline hemiacetals corytensine and egenine, confirming the previously assigned structures and absolute configurations, and establishing the identity of egenine with decumbensine and of corytensine with epi-alpha-decumbensine.