(1R,4R)-8-methoxy-1-methyl-2,3,4,5-tetrahydro-1,4-methano-3-benzazepine | 620163-18-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯氮卓类
• 英文名称: (1R,4R)-8-methoxy-1-methyl-2,3,4,5-tetrahydro-1,4-methano-3-benzazepine
• 英文别名: (1R,4S)-1-methyl-8-methoxy-2,3,4,5-tetrahydro-1,4-methano-3-benzazepine；(1R,9R)-4-methoxy-1-methyl-10-azatricyclo[7.2.1.02,7]dodeca-2(7),3,5-triene
• CAS: 620163-18-0
• 化学式: C₁₃H₁₇NO
• 分子量: 203.284
• InChiKey: HXDJRNVUXYQONU-MFKMUULPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  21.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,4R)-8-methoxy-1-methyl-2,3,4,5-tetrahydro-1,4-methano-3-benzazepine 在 甲酸 、 三溴化硼 作用下， 以 二氯甲烷 为溶剂， 反应 3.5h， 生成 (+/-)-aphanorphine
  参考文献：
  名称：

  Asymmetric Synthesis of Benzylic Quaternary Carbon Center via an Enzymatic Reaction

  摘要：

  (R)-(+)-((R)-(+)-12) and (S)-(-)-1-formyl-1-methyl-7-methoxy-1,2,3,4-tetrahydronaphthalene ((S)-(-)-12) were synthesized based on enantioselective PLE hydrolysis of diethyl 2-(m-methoxyphenyl)-2-methylmalonate. From (R)-(+)-12, (+)-O-Methylaphanorphine (16) and (-)-aphanorphine were synthesized. (S)-(+)-1-(N-Acetyl-N-methylaminoethyl)-1-methyl-7-methoxytetralin (25) was synthesized from (S)-(-)-12. This transformation constitutes a formal synthesis of (-)-eptazocine.

  DOI：

  10.3987/com-96-7421
• 作为产物：
  描述：

  3-甲氧基苯基乙酸乙酯 在 platinum(IV) oxide 、 palladium on activated charcoal 盐酸 、 potassium dichromate 、 sodium hydroxide 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 锂硼氢 、 高氯酸 、 Celite 、 pH 8.04 phosphate buffer 、 硫酸 、 盐酸羟胺 、 氢气 、 溴 、 sodium methylate 、 sodium acetate 、 sodium hydride 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 乙二醇二甲醚 、 乙醇 、 二氯甲烷 、 水 、 溶剂黄146 、 丙酮 、 paraffin 、 苯 为溶剂， 反应 302.83h， 生成 (1R,4R)-8-methoxy-1-methyl-2,3,4,5-tetrahydro-1,4-methano-3-benzazepine
  参考文献：
  名称：

  Asymmetric Synthesis of Benzylic Quaternary Carbon Center via an Enzymatic Reaction

  摘要：

  (R)-(+)-((R)-(+)-12) and (S)-(-)-1-formyl-1-methyl-7-methoxy-1,2,3,4-tetrahydronaphthalene ((S)-(-)-12) were synthesized based on enantioselective PLE hydrolysis of diethyl 2-(m-methoxyphenyl)-2-methylmalonate. From (R)-(+)-12, (+)-O-Methylaphanorphine (16) and (-)-aphanorphine were synthesized. (S)-(+)-1-(N-Acetyl-N-methylaminoethyl)-1-methyl-7-methoxytetralin (25) was synthesized from (S)-(-)-12. This transformation constitutes a formal synthesis of (-)-eptazocine.

  DOI：

  10.3987/com-96-7421

文献信息

• Concise Route to (-)- and (+)-Aphanorphine
  作者：Mohamed Medjahdi、José C. González-Gómez、Francisco Foubelo、Miguel Yus

  DOI：10.1002/ejoc.201100091

  日期：2011.4

  presents an application of two recently developed methodologies to the synthesis of naturally occurring (–)-aphanorphine. The first method involves an indium-mediated stereoselective α-aminoallylation of aldehydes to prepare enantioenriched homoallylic amine derivatives. The second is the epoxidation and regioselective opening of the epoxide to afford 2-substituted 3-pyrrolidinols. The synthesis was completed

  本文介绍了两种最近开发的方法在天然存在的 (-)-aphanorphine 合成中的应用。第一种方法涉及醛的铟介导立体选择性α-氨基烯丙基化，以制备对映体富集的高烯丙基胺衍生物。第二个是环氧化物的环氧化和区域选择性打开以提供 2-取代的 3-吡咯烷醇。合成是通过使用报道的 Friedel-Crafts 烷基化和传统的官能团操作完成的。按照同样的路线，由(S)-2-甲基丙烷-2-亚磺酰胺制备了非天然(+)-aphanorphine的O-甲基衍生物。
• A Facile Asymmetric Route to (−)-Aphanorphine
  作者：Hongbin Zhai、Shengjun Luo、Chengfeng Ye、Yongxiang Ma

  DOI：10.1021/jo0348726

  日期：2003.10.1

  8O-methylaphanorphine was synthesized from 4-methoxyphenylacetaldehyde in 36% overall yield and in nine steps, featuring the formation of ring B via a Friedel-Crafts alkylative cyclization with the concomitant stereospecific introduction of the benzylic quaternary carbon center. The current work constitutes an efficient enantioselective formal synthesis of 3-benzazepine marine alkaloid (-)-aphanorphine

  由4-甲氧基苯基乙醛以36％的总收率和九个步骤合成8O-甲基甲啡烷，其特征在于通过Friedel-Crafts烷基化环化并伴随立体定向引入苄基季碳中心形成环B。目前的工作构成了3-苯并ze庚因海洋生物碱（-）-甲啡肽的有效对映选择性形式合成。
• Asymmetric Synthesis of Benzylic Quaternary Carbon Center via an Enzymatic Reaction
  作者：Shunsaku Shiotani、Hirohiko Okada、Kumiko Nakamata、Takako Yamamoto、Fumie Sekino

  DOI：10.3987/com-96-7421

  日期：——

  (R)-(+)-((R)-(+)-12) and (S)-(-)-1-formyl-1-methyl-7-methoxy-1,2,3,4-tetrahydronaphthalene ((S)-(-)-12) were synthesized based on enantioselective PLE hydrolysis of diethyl 2-(m-methoxyphenyl)-2-methylmalonate. From (R)-(+)-12, (+)-O-Methylaphanorphine (16) and (-)-aphanorphine were synthesized. (S)-(+)-1-(N-Acetyl-N-methylaminoethyl)-1-methyl-7-methoxytetralin (25) was synthesized from (S)-(-)-12. This transformation constitutes a formal synthesis of (-)-eptazocine.