13β-O-methoxymethyl-5-O-tert-butydimethylsilyl-7-O-trimethylsilyl-22,23-dihydroavermectin B1 aglycon | 190435-15-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: 13β-O-methoxymethyl-5-O-tert-butydimethylsilyl-7-O-trimethylsilyl-22,23-dihydroavermectin B1 aglycon
• 英文别名: (1R,4S,5'S,6R,6'R,8R,10E,12R,13S,14E,16E,20R,21R,24S)-6'-[(2S)-butan-2-yl]-21-[tert-butyl(dimethyl)silyl]oxy-12-(methoxymethoxy)-5',11,13,22-tetramethyl-24-trimethylsilyloxyspiro[3,7,19-trioxatetracyclo[15.6.1.14,8.020,24]pentacosa-10,14,16,22-tetraene-6,2'-oxane]-2-one
• CAS: 190435-15-5
• 化学式: C₄₅H₇₆O₉Si₂
• 分子量: 817.264
• InChiKey: KGGLVFHSVXYGEK-QISSGGPPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.05
• 重原子数：
  56.0
• 可旋转键数：
  9.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  90.91
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  13β-O-methoxymethyl-5-O-tert-butydimethylsilyl-7-O-trimethylsilyl-22,23-dihydroavermectin B1 aglycon 在 盐酸 作用下， 以 甲醇 为溶剂， 反应 2.5h， 以98%的产率得到13β-O-methoxymethyl-22,23-dihydroavermectin B1 aglycon
  参考文献：
  名称：

  Practical Syntheses of 13-O-[(2-Methoxyethoxy)methyl]-22,23-dihydroavermectin B₁ Aglycon [Dimedectin Isopropanol, MK-324] and 13-epi-O-(Methoxymethyl)-22,23-dihydroavermectin B₁ Aglycon [L-694,554], Flea Active Ivermectin Analogues

  摘要：

  Practical high yielding syntheses of 13-O-[(2-methoxyethoxy)methyl]-22,23-dihydroavermectin B-1 aglycon (dimedectin 2-propanol, MK-324, 1) and 13-epi-O-(methoxymethyl)-22,23-dihydroavermectin B-1 aglycon (L-694,554, 2), both potent flea insecticides, from ivermectin are presented. The successful selective manipulation of silyl protecting groups on ivermectin aglycon led to the facile preparation of 5,7-O-bis-silyl-22,23-dihydroavermectin B-1 aglycon 7 as the key intermediate for the large scale syntheses of these compounds. Development of a dual pyridine/tertiary amine system for mesylation of the C-13 alpha hydroxyl group of 7 and subsequent displacement with cesium propionate-propionic acid led to the successful inversion of the 13-hydroxy group.

  DOI：

  10.1021/jo970187l
• 作为产物：
  描述：

  13α-O-mesyl-5-O-tert-butydimethylsilyl-7-O-trimethylsilyl-22,23-dihydroavermectin B1 aglycon 在 咪唑 、 titanium(IV) isopropylate 、 三甲基氯硅烷 、 18-冠醚-6 、 caesium carbonate 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 异丙醇 为溶剂， 反应 57.42h， 生成 13β-O-methoxymethyl-5-O-tert-butydimethylsilyl-7-O-trimethylsilyl-22,23-dihydroavermectin B1 aglycon
  参考文献：
  名称：

  Practical Syntheses of 13-O-[(2-Methoxyethoxy)methyl]-22,23-dihydroavermectin B₁ Aglycon [Dimedectin Isopropanol, MK-324] and 13-epi-O-(Methoxymethyl)-22,23-dihydroavermectin B₁ Aglycon [L-694,554], Flea Active Ivermectin Analogues

  摘要：

  Practical high yielding syntheses of 13-O-[(2-methoxyethoxy)methyl]-22,23-dihydroavermectin B-1 aglycon (dimedectin 2-propanol, MK-324, 1) and 13-epi-O-(methoxymethyl)-22,23-dihydroavermectin B-1 aglycon (L-694,554, 2), both potent flea insecticides, from ivermectin are presented. The successful selective manipulation of silyl protecting groups on ivermectin aglycon led to the facile preparation of 5,7-O-bis-silyl-22,23-dihydroavermectin B-1 aglycon 7 as the key intermediate for the large scale syntheses of these compounds. Development of a dual pyridine/tertiary amine system for mesylation of the C-13 alpha hydroxyl group of 7 and subsequent displacement with cesium propionate-propionic acid led to the successful inversion of the 13-hydroxy group.

  DOI：

  10.1021/jo970187l

文献信息

• Methoxymethylation of Alcohols, Phenols, and Avermectin Aglycones Using MOM-2-pyridylsulfide
  作者：Benjamin F. Marcune、Sandor Karady、Ulf-H. Dolling、Thomas J. Novak

  DOI：10.1021/jo9822582

  日期：1999.4.1

  Methoxymethyl-2-pyridylsulfide (MOM-ON) is an effective methoxymethylating reagent when used in conjunction with AgOTf, NaOAc, and THF. A wide range of MOM ethers are produced from corresponding phenols and alcohols, including tertiary and allylic alcohols, in good yields and under mild, neutral conditions. This method is also effective for the methoxymethylation of avermectin aglycones.