(S)-1,2,3,4-tetrahydro-6,7-dimethoxy-2-<<(1-(methoxymethyl)-2-methoxypropyl)imino>methyl>isoquinoline | 162147-23-1

• 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: (S)-1,2,3,4-tetrahydro-6,7-dimethoxy-2-<<(1-(methoxymethyl)-2-methoxypropyl)imino>methyl>isoquinoline
• 英文别名: (S)-1,2,3,4-tetrahydro-6,7-dimethoxy-2-[[(1-(methoxymethyl)-2-methylpropyl)imino]methyl]isoquinoline；1-(6,7-dimethoxy-3,4-dihydro-1H-isoquinolin-2-yl)-N-[(2S)-1-methoxy-3-methylbutan-2-yl]methanimine
• CAS: 162147-23-1
• 化学式: C₁₈H₂₈N₂O₃
• 分子量: 320.432
• InChiKey: BZTHPLPFCLKXLK-MRXNPFEDSA-N

物化性质

• 沸点：
  433.7±55.0 °C(predicted)
• 密度：
  1.08±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  43.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-1,2,3,4-tetrahydro-6,7-dimethoxy-2-<<(1-(methoxymethyl)-2-methoxypropyl)imino>methyl>isoquinoline 在 正丁基锂 、 一水合肼 、 溶剂黄146 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 为溶剂， 反应 12.0h， 生成 (S)-1,2,3,4-tetrahydro-6,7-dimethoxy-1-[(3,4-methylenedioxy-2-trimethylsilylphenyl)methyl]isoquinoline
  参考文献：
  名称：

  Synthesis of protoberberines using a silyl-directed Pictet–Spengler cyclization

  摘要：

  Five naturally-occurring protoberberines have been synthesized in enantioenriched form by alkylation by two different 2-trimethylsilylbenzyl chlorides of four tetrahydroisoquinolines, derivatized with Meyers' formamidine valinol methyl ether chiral auxiliary. Silyl-directed Pictet-Spengler cyclization of the ensuing 3,4-dimethoxy-2-trimethylsilylbenzyl tetrahydroisoquinolines leads to four of the target protoberberines in excellent yield and complete regioselectivity. In the fifth case, the 3,4-methylenedioxy analog gives a mixture of protoberberine and a product of ring closure at C6 of the benzyl moiety in a 3:4 ratio. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(02)00010-8
• 作为产物：
  描述：

  1,2-dimethoxy-4-(2-nitro-vinyl)-benzene 在 ammonium sulfate 、 lithium aluminium tetrahydride 、 甲酸 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 42.0h， 生成 (S)-1,2,3,4-tetrahydro-6,7-dimethoxy-2-<<(1-(methoxymethyl)-2-methoxypropyl)imino>methyl>isoquinoline
  参考文献：
  名称：

  Synthesis of protoberberines using a silyl-directed Pictet–Spengler cyclization

  摘要：

  Five naturally-occurring protoberberines have been synthesized in enantioenriched form by alkylation by two different 2-trimethylsilylbenzyl chlorides of four tetrahydroisoquinolines, derivatized with Meyers' formamidine valinol methyl ether chiral auxiliary. Silyl-directed Pictet-Spengler cyclization of the ensuing 3,4-dimethoxy-2-trimethylsilylbenzyl tetrahydroisoquinolines leads to four of the target protoberberines in excellent yield and complete regioselectivity. In the fifth case, the 3,4-methylenedioxy analog gives a mixture of protoberberine and a product of ring closure at C6 of the benzyl moiety in a 3:4 ratio. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(02)00010-8

文献信息

• Total Synthesis of (−)-Tetrahydropalmatine via Chiral Formamidine Carbanions:  Unexpected Behavior with Certain Ortho-Substituted Electrophiles
  作者：Mark A. Matulenko、A. I. Meyers

  DOI：10.1021/jo951611q

  日期：1996.1.1

  established using an ortho-substituted hydroxymethylbenzene electrophile protected as a silyl ether to ultimately provide (-)-tetrahydropalmatine in 88% ee. Additionally, we have discovered limitations with ortho-substituted electrophiles in the asymmetric formamidine alkylation. These electrophiles have the potential to disrupt the lithium formamidine chelate and cause the selectivity in the alkylation to

  已经开发出一种通过手性硫代甲alkyl的烷基化来构建具有C（9）和C（10）D环取代模式的原小ber碱生物碱的方法。使用被保护为甲硅烷基醚的邻位取代的羟甲基苯亲电子试剂建立该环型，以最终提供88％ee的（-）-四氢巴马汀。此外，我们发现在不对称甲am烷基化反应中邻位取代的亲电试剂存在局限性。这些亲电试剂具有破坏甲form酸锂螯合物的潜力，并导致烷基化反应的选择性异常低。本文描述了（+/-）-犬精和（-）-四氢巴马汀的总合成以及对甲am烷基化技术的限制。
• Synthesis of protoberberines using a silyl-directed Pictet–Spengler cyclization
  作者：Paul S Cutter、R.Bryan Miller、Neil E Schore

  DOI：10.1016/s0040-4020(02)00010-8

  日期：2002.2

  Five naturally-occurring protoberberines have been synthesized in enantioenriched form by alkylation by two different 2-trimethylsilylbenzyl chlorides of four tetrahydroisoquinolines, derivatized with Meyers' formamidine valinol methyl ether chiral auxiliary. Silyl-directed Pictet-Spengler cyclization of the ensuing 3,4-dimethoxy-2-trimethylsilylbenzyl tetrahydroisoquinolines leads to four of the target protoberberines in excellent yield and complete regioselectivity. In the fifth case, the 3,4-methylenedioxy analog gives a mixture of protoberberine and a product of ring closure at C6 of the benzyl moiety in a 3:4 ratio. (C) 2002 Published by Elsevier Science Ltd.