(8R*,14S*)-(+/-)-8-hydroxymethylcanadine

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 原小檗碱生物碱及其衍生物
• 英文名称: (8R*,14S*)-(+/-)-8-hydroxymethylcanadine
• 英文别名: [(1S,14R)-16,17-dimethoxy-5,7-dioxa-13-azapentacyclo[11.8.0.02,10.04,8.015,20]henicosa-2,4(8),9,15(20),16,18-hexaen-14-yl]methanol
• 化学式: C₂₁H₂₃NO₅
• 分子量: 369.417
• InChiKey: SCOXMKSUPJEJMB-HOTGVXAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  60.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  盐酸小檗碱 在 盐酸 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 Amberlite IR-120 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 62.0h， 生成 (8R*,14S*)-(+/-)-8-hydroxymethylcanadine
  参考文献：
  名称：

  小b碱N-氧化物的Polonovski-Potier反应。8-羟甲基和8-甲基berbines的合成

  摘要：

  的Polonovski-博天反应反式和顺berbines Ñ -oxides进行了研究。由反式N-氧化物获得的8-氰基衍生物用于合成8-羟甲基和8-甲基小碱。将该方法应用于从（14 S）-（-）-犬精的立体控制合成（8 R，14 S）-（-）-8-甲基犬精。

  DOI：

  10.1016/s0040-4020(00)00945-5

文献信息

• Photochemical hydroxymethylation of protoberberine alkaloids. Total synthesis of (±)-solidaline
  作者：Rafael Suau、Francisco Nájera、Rodrigo Rico

  DOI：10.1016/0040-4039(96)00625-9

  日期：1996.5

  berberinium salts was readily achieved by photoaddition of methanol. The resulting photoproducts were isolated as tetrahydroprotoberberine derivatives. By combining this photochemical reaction with the oxidation of the photoproduct, the synthesis of (±)-solidaline starting from palmatine chloride was accomplished for the first time.

  通过甲醇的光加成很容易地在小salts盐的C-8位上引入羟甲基。分离得到的光产物为四氢小ber碱衍生物。通过将该光化学反应与光产物的氧化相结合，首次完成了从氯化棕榈酰开始的（±）-固醇的合成。
• Hydroxymethylation of protoberberine alkaloids by photoinduced SET. The total synthesis of (±)-solidaline
  作者：Rafael Suau、Francisco Nájera、Rodrigo Rico

  DOI：10.1016/s0040-4020(99)00090-3

  日期：1999.3

  The direct insertion of a hydroxymethyl group at position C-8 in a protoberberinium ion by photoaddition of methanol was approached via two mechanistic pathways: acetone-sensitized and single-electron transfer. The latter produces 8-hydroxymethylberbines in good yields after reduction. By combining this photochemical reaction with the oxidation of the photoproduct, syntheses of (+/-)-solidaline and its C-13 epimer from palmatine chloride were accomplished for the first time. On the other hand, insertion of a hydroxymethyl group at position 14 of the berberine skeleton in order to open a synthetic pathway for zijinlongine proved unsuccessful. (C) 1999 Elsevier Science Ltd. All rights reserved.
• The Polonovski–Potier Reaction of Berbine N-Oxides. Synthesis of 8-Hydroxymethyl and 8-Methylberbines
  作者：Rafael Suau、Francisco Nájera、Rodrigo Rico

  DOI：10.1016/s0040-4020(00)00945-5

  日期：2000.12

  The Polonovski–Potier reaction of trans and cis berbines N-oxides was studied. The 8-cyano derivative obtained from transN-oxides were used to synthesize 8-hydroxymethyl and 8-methyl berbines. This procedure was applied to the stereocontroled synthesis of (8R, 14S)-(−)-8-methylcanadine from (14S)-(−)-canadine.

  的Polonovski-博天反应反式和顺berbines Ñ -oxides进行了研究。由反式N-氧化物获得的8-氰基衍生物用于合成8-羟甲基和8-甲基小碱。将该方法应用于从（14 S）-（-）-犬精的立体控制合成（8 R，14 S）-（-）-8-甲基犬精。