(2S)-(-)-3,4-dimethyl-2-(phenylmethyl)-1-<(1R)-1-phenylethyl>-1,2,5,6-tetrahydropyridine | 146099-04-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (2S)-(-)-3,4-dimethyl-2-(phenylmethyl)-1-<(1R)-1-phenylethyl>-1,2,5,6-tetrahydropyridine
• 英文别名: (6S)-6-benzyl-4,5-dimethyl-1-[(1R)-1-phenylethyl]-3,6-dihydro-2H-pyridine
• CAS: 146099-04-9
• 化学式: C₂₂H₂₇N
• 分子量: 305.463
• InChiKey: YBYGBXYYYOLNNS-KNQAVFIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2S)-(-)-3,4-dimethyl-2-(phenylmethyl)-1-<(1R)-1-phenylethyl>-1,2,5,6-tetrahydropyridine 在 palladium on activated charcoal 盐酸 、 磷酸 、 氢气 、 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 乙醇 、 乙酸乙酯 为溶剂， 反应 61.0h， 生成 (1S,5S,9S)-(+)-5,9-dimethyl-2-methyl-6,7-benzomorphan
  参考文献：
  名称：

  A stereocontrolled alkylation of chiral pyridinium salts with Grignard reagents: synthesis of (+)-normetazocine and (+)-nordextrorphan

  摘要：

  The synthesis of chiral pyridinium salts 3, bearing lipophilic counteranions, is described. These salts, soluble in THF or toluene, undergo nucleophilic alkylation with benzylic Grignard reagents to give, after reduction of the unstable dihydropyridine intermediates, adducts 4 with regio- and stereoselective attack at position 2, the observed stereoselectivity ranging from 8:1 to 12.5:1. These results allowed an asymmetric synthesis, following Grewe's route, of (+)-normetazocine and (+)-nordextrorphan, key precursors of various benzomorphan or morphinan drugs.

  DOI：

  10.1021/jo00060a019
• 作为产物：
  描述：

  苄基溴化镁 、 (+)-3,4-dimethyl-1-<(1R)-1-phenylethyl>pyridinium dodecylsulfate 在 sodium tetrahydroborate 作用下， 生成 (2S)-(-)-3,4-dimethyl-2-(phenylmethyl)-1-<(1R)-1-phenylethyl>-1,2,5,6-tetrahydropyridine
  参考文献：
  名称：

  A stereocontrolled alkylation of chiral pyridinium salts with Grignard reagents: synthesis of (+)-normetazocine and (+)-nordextrorphan

  摘要：

  The synthesis of chiral pyridinium salts 3, bearing lipophilic counteranions, is described. These salts, soluble in THF or toluene, undergo nucleophilic alkylation with benzylic Grignard reagents to give, after reduction of the unstable dihydropyridine intermediates, adducts 4 with regio- and stereoselective attack at position 2, the observed stereoselectivity ranging from 8:1 to 12.5:1. These results allowed an asymmetric synthesis, following Grewe's route, of (+)-normetazocine and (+)-nordextrorphan, key precursors of various benzomorphan or morphinan drugs.

  DOI：

  10.1021/jo00060a019

文献信息

• A stereocontrolled alkylation of chiral pyridinium salts with Grignard reagents: synthesis of (+)-normetazocine and (+)-nordextrorphan
  作者：Yves Genisson、Christian Marazano、Bhupesh C. Das

  DOI：10.1021/jo00060a019

  日期：1993.4

  The synthesis of chiral pyridinium salts 3, bearing lipophilic counteranions, is described. These salts, soluble in THF or toluene, undergo nucleophilic alkylation with benzylic Grignard reagents to give, after reduction of the unstable dihydropyridine intermediates, adducts 4 with regio- and stereoselective attack at position 2, the observed stereoselectivity ranging from 8:1 to 12.5:1. These results allowed an asymmetric synthesis, following Grewe's route, of (+)-normetazocine and (+)-nordextrorphan, key precursors of various benzomorphan or morphinan drugs.