(4''S)-4''-desdimethylamino-4''-(methanesulfonyloxy)spinosyn A | 849420-51-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4''S)-4''-desdimethylamino-4''-(methanesulfonyloxy)spinosyn A
• 英文别名: [(2R,3S,6R)-6-[[(1S,2R,5S,7R,9R,10S,14R,15S,19S)-19-ethyl-14-methyl-13,21-dioxo-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-dien-15-yl]oxy]-2-methyloxan-3-yl] methanesulfonate
• CAS: 849420-51-5
• 化学式: C₄₀H₆₂O₁₃S
• 分子量: 782.99
• InChiKey: LFOVSGPIZDOEMH-KXRJSVEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  54
• 可旋转键数：
  10
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  160
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  (4''S)-4''-desdimethylamino-4''-(methanesulfonyloxy)spinosyn A 在 sodium azide 、 tin(ll) chloride 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 23.0h， 生成 (1S,2R,5S,7R,9R,10S,14R,15S,19S)-15-[(2R,5R,6R)-5-amino-6-methyloxan-2-yl]oxy-19-ethyl-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
  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：

  多杀菌素 在 吡啶 、 1-chloromethyl-4-fluorotriethylenediamine tetrafluoroborate 、 lithium tri-t-butoxyaluminum hydride 、 N,N-二异丙基乙胺 作用下， 以 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 乙腈 为溶剂， 反应 2.17h， 生成 (4''S)-4''-desdimethylamino-4''-(methanesulfonyloxy)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

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.