(4''S)-4''-desdimethylamino-4''-hydroxyspinosyn A | 187168-79-2

• 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: (4''S)-4''-desdimethylamino-4''-hydroxyspinosyn A
• 英文别名: (1S,2R,5S,7R,9R,10S,14R,15S,19S)-19-ethyl-15-[(2R,5S,6R)-5-hydroxy-6-methyloxan-2-yl]oxy-14-methyl-7-[(2R,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyloxan-2-yl]oxy-20-oxatetracyclo[10.10.0.02,10.05,9]docosa-3,11-diene-13,21-dione
• CAS: 187168-79-2
• 化学式: C₃₉H₆₀O₁₁
• 分子量: 704.899
• InChiKey: HGJQJKQDNRFFSI-PNXRJMMDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  50
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  128
• 氢给体数：
  1
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  (4''S)-4''-desdimethylamino-4''-hydroxyspinosyn A 在 吡啶 、 sodium azide 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 生成 (4''R)-4''-desdimethylamino-4''-(azido)spinosyn A
  参考文献：
  名称：

  Spinosyn G:  Proof of Structure by Semisynthesis

  摘要：

  Spinosyn G was isolated in the late 1980s as a minor component from the broth of our potent, fermentation-derived insecticide spinosad. Its structure was then tentatively identified as 5"-epispinosyn A (3) on the basis of H-1 and C-13 NMR data, but the 4"-epi compound 4 could not be conclusively ruled out with the data available. Described herein are unambiguous syntheses of both 3 and 4, whereby 3 was proved identical to the natural product. Compound 4 was prepared from intact spinosyn A by a novel F-TEDA-promoted oxidative deamination to the 4"-ketone 5, stereoselective reduction to the equatorial alcohol 6, and nitrogen incorporation via the axial azide 7. Compound 3 was obtained by coupling spinosyn A 17-pseudoaglycone (9) with the N-protected dihydropyran 16 derived from methyl L-ossaminide (14). This gave an similar to 2:1 mixture of anomeric products 17 with the desired equatorial glycoside predominating, which was then converted to 3 by N-deprotection and methylation.

  DOI：

  10.1021/jo048173k
• 作为产物：
  描述：

  4''-ketospinosyn A 在 lithium tri-t-butoxyaluminum hydride 作用下， 以 1,4-二氧六环 、 乙醚 为溶剂， 反应 0.17h， 以99%的产率得到(4''S)-4''-desdimethylamino-4''-hydroxyspinosyn A
  参考文献：
  名称：

  Spinosyn G:  Proof of Structure by Semisynthesis

  摘要：

  Spinosyn G was isolated in the late 1980s as a minor component from the broth of our potent, fermentation-derived insecticide spinosad. Its structure was then tentatively identified as 5"-epispinosyn A (3) on the basis of H-1 and C-13 NMR data, but the 4"-epi compound 4 could not be conclusively ruled out with the data available. Described herein are unambiguous syntheses of both 3 and 4, whereby 3 was proved identical to the natural product. Compound 4 was prepared from intact spinosyn A by a novel F-TEDA-promoted oxidative deamination to the 4"-ketone 5, stereoselective reduction to the equatorial alcohol 6, and nitrogen incorporation via the axial azide 7. Compound 3 was obtained by coupling spinosyn A 17-pseudoaglycone (9) with the N-protected dihydropyran 16 derived from methyl L-ossaminide (14). This gave an similar to 2:1 mixture of anomeric products 17 with the desired equatorial glycoside predominating, which was then converted to 3 by N-deprotection and methylation.

  DOI：

  10.1021/jo048173k

文献信息

• Spinosyn G:  Proof of Structure by Semisynthesis
  作者：Paul R. Graupner、Jacek Martynow、Peter B. Anzeveno

  DOI：10.1021/jo048173k

  日期：2005.3.1

  Spinosyn G was isolated in the late 1980s as a minor component from the broth of our potent, fermentation-derived insecticide spinosad. Its structure was then tentatively identified as 5"-epispinosyn A (3) on the basis of H-1 and C-13 NMR data, but the 4"-epi compound 4 could not be conclusively ruled out with the data available. Described herein are unambiguous syntheses of both 3 and 4, whereby 3 was proved identical to the natural product. Compound 4 was prepared from intact spinosyn A by a novel F-TEDA-promoted oxidative deamination to the 4"-ketone 5, stereoselective reduction to the equatorial alcohol 6, and nitrogen incorporation via the axial azide 7. Compound 3 was obtained by coupling spinosyn A 17-pseudoaglycone (9) with the N-protected dihydropyran 16 derived from methyl L-ossaminide (14). This gave an similar to 2:1 mixture of anomeric products 17 with the desired equatorial glycoside predominating, which was then converted to 3 by N-deprotection and methylation.