-α-1,3-benzodioxol-5-yl-5,6,7,8-tetrahydro-6-(2,2-dimethyl-1-oxopropyl)-1,3-dioxolo<4,5-g>isoquinoline-5-methanol | 131589-14-5

• 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-(2,2-dimethyl-1-oxopropyl)-1,3-dioxolo<4,5-g>isoquinoline-5-methanol
• 英文别名: 1-[(5R)-5-[(S)-1,3-benzodioxol-5-yl(hydroxy)methyl]-7,8-dihydro-5H-[1,3]dioxolo[4,5-g]isoquinolin-6-yl]-2,2-dimethylpropan-1-one
• CAS: 131589-14-5
• 化学式: C₂₃H₂₅NO₆
• 分子量: 411.455
• InChiKey: RXHRRMLYFWIPKI-RTWAWAEBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.35
• 重原子数：
  30.0
• 可旋转键数：
  2.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  77.46
• 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-(2,2-dimethyl-1-oxopropyl)-1,3-dioxolo<4,5-g>isoquinoline-5-methanol 在 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 正丁基锂 、 三氟乙酸酐 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 32.0h， 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：

  三甲基乙酰氯 、 -α-1,3-benzodioxol-5-yl-5,6,7,8-tetrahydro-1,3-dioxolo<4,5-g>isoquinoline-5-methyl L-tartrate 在 sodium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以87%的产率得到-α-1,3-benzodioxol-5-yl-5,6,7,8-tetrahydro-6-(2,2-dimethyl-1-oxopropyl)-1,3-dioxolo<4,5-g>isoquinoline-5-methanol
  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

文献信息

• 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：——