-α-1,3-benzodioxol-5-yl-5,6,7,8-tetrahydro-6-methyl-1,3-dioxolo<4,5-g>isoquinoline-5-methanol | 131681-58-8

• 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: -α-1,3-benzodioxol-5-yl-5,6,7,8-tetrahydro-6-methyl-1,3-dioxolo<4,5-g>isoquinoline-5-methanol
• 英文别名: epi-α-decumbensine；(R)-1,3-benzodioxol-5-yl-[(5R)-6-methyl-7,8-dihydro-5H-[1,3]dioxolo[4,5-g]isoquinolin-5-yl]methanol
• CAS: 131681-58-8
• 化学式: C₁₉H₁₉NO₅
• 分子量: 341.364
• InChiKey: BIAJOCGDBRRARC-RTBURBONSA-N

物化性质

• 熔点：
  115.5-117.5 °C
• 沸点：
  501.6±50.0 °C(Predicted)
• 密度：
  1.386±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.41
• 重原子数：
  25.0
• 可旋转键数：
  2.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  60.39
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  -α-1,3-benzodioxol-5-yl-5,6,7,8-tetrahydro-6-methyl-1,3-dioxolo<4,5-g>isoquinoline-5-methanol 在 sodium tetrahydroborate 、 正丁基锂 作用下， 以 乙醇 为溶剂， 反应 2.0h， 生成 adlumidinediol
  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：

  胡椒乙胺 在 platinum(IV) oxide 吡啶 、 盐酸 、 sodium periodate 、 正丁基锂 、 五氯化磷 、 氢气 、 sodium methylate 、 sodium acetate 、 sodium cyanoborohydride 、 溶剂黄146 、 间氯过氧苯甲酸 作用下， 以 1,4-二氧六环 、 甲醇 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 26.59h， 生成 -α-1,3-benzodioxol-5-yl-5,6,7,8-tetrahydro-6-methyl-1,3-dioxolo<4,5-g>isoquinoline-5-methanol
  参考文献：
  名称：

  Czarnocki, Zbigniew, Journal of Chemical Research, Miniprint, 1992, # 12, p. 3101 - 3116

  摘要：

  DOI：

文献信息

• ROZWADOWSKA, MARIA D.;MATECKA, DOROTA;BROZDA, DANUTA, TETRAHEDRON LETT., 30,(1989) N5, C. 6215-6218
  作者：ROZWADOWSKA, MARIA D.、MATECKA, DOROTA、BROZDA, DANUTA

  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：——
• Czarnocki, Zbigniew, Journal of Chemical Research, Miniprint, 1992, # 12, p. 3101 - 3116
  作者：Czarnocki, Zbigniew

  DOI：——

  日期：——
• 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.