4-Methoxy-3-((R)-2-{(1R,2R,6S)-2-[(E)-2-((2S,3S,6R)-6-{(E)-3-[(2S,5S)-5-((R)-1-methoxy-ethyl)-tetrahydro-furan-2-yl]-propenyl}-3-methyl-tetrahydro-pyran-2-yl)-3-triethylsilanyloxy-propenyl]-6-methyl-cyclohexyl}-propionyl)-5-methylene-5H-furan-2-one | 142459-48-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-Methoxy-3-((R)-2-{(1R,2R,6S)-2-[(E)-2-((2S,3S,6R)-6-{(E)-3-[(2S,5S)-5-((R)-1-methoxy-ethyl)-tetrahydro-furan-2-yl]-propenyl}-3-methyl-tetrahydro-pyran-2-yl)-3-triethylsilanyloxy-propenyl]-6-methyl-cyclohexyl}-propionyl)-5-methylene-5H-furan-2-one
• CAS: 142459-48-1
• 化学式: C₄₁H₆₆O₈Si
• 分子量: 715.056
• InChiKey: YLFLJOMCVLJVTH-WKCWLBIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.88
• 重原子数：
  50.0
• 可旋转键数：
  17.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  89.52
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  4-Methoxy-3-((R)-2-{(1R,2R,6S)-2-[(E)-2-((2S,3S,6R)-6-{(E)-3-[(2S,5S)-5-((R)-1-methoxy-ethyl)-tetrahydro-furan-2-yl]-propenyl}-3-methyl-tetrahydro-pyran-2-yl)-3-triethylsilanyloxy-propenyl]-6-methyl-cyclohexyl}-propionyl)-5-methylene-5H-furan-2-one 在 氢氟酸 作用下， 以 乙腈 为溶剂， 反应 0.08h， 以12.7 mg的产率得到3-((R)-2-{(1R,2R,6S)-2-[(E)-3-Hydroxy-2-((2S,3S,6R)-6-{(E)-3-[(2S,5S)-5-((R)-1-methoxy-ethyl)-tetrahydro-furan-2-yl]-propenyl}-3-methyl-tetrahydro-pyran-2-yl)-propenyl]-6-methyl-cyclohexyl}-propionyl)-4-methoxy-5-methylene-5H-furan-2-one
  参考文献：
  名称：

  Total synthesis of tetronomycin

  摘要：

  The first total synthesis of (+)-tetronomycin (1), a novel tetronic acid ionophore antibiotic, has been achieved through the synthesis and assemblage of the four cyclic segments 4, 5, 7, and 8. Construction of the C5-C-13 cyclohexyl portion 5 involves as the key step either a Beckmann fragmentation of the bicyclic ketone oxime 45 or an L-Selectride-mediated reductive annulation of the nona-2,7-dienoate 53. The C-14-C28 polyether fragment 6 was constructed by a BF3-catalyzed coupling reaction of the C-14-C22 allylsilane 7 and the C23-C28 tetrahydrofuran 8 which were derived, respectively, from L-ascorbic acid or (R)-3-hydroxyisobutyrate and L-rhamnal. The union of 5 and 6 by an aldol condensation, followed by photoisomerization of the derived diastereomeric alpha,beta-unsaturated esters, provided (Z)-61, which was converted to the aldehyde 63. Subsequent acylation of the tetronate 4 with 63 via an aldol reaction-oxidation sequence afforded the protected tetronomycin 64. Final deprotection provided synthetic tetronomycin, which was characterized as its sodium salt.

  DOI：

  10.1021/jo00036a026
• 作为产物：
  描述：

  (E)-(4R,5S)-4-Acetoxy-5-(methanesulfonyloxy)-2-hexenal 在 palladium on activated charcoal 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 N,N-二甲基丙烯基脲 、 sodium chlorite 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 草酰氯 、 4 A molecular sieve 、 三氟化硼乙醚 、 四丁基氟化铵 、 氢气 、 sodium hydride 、 二异丁基氢化铝 、 二甲基亚砜 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 pyridinium chlorochromate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 丙酮 、 甲苯 、 叔丁醇 为溶剂， 反应 118.81h， 生成 4-Methoxy-3-((R)-2-{(1R,2R,6S)-2-[(E)-2-((2S,3S,6R)-6-{(E)-3-[(2S,5S)-5-((R)-1-methoxy-ethyl)-tetrahydro-furan-2-yl]-propenyl}-3-methyl-tetrahydro-pyran-2-yl)-3-triethylsilanyloxy-propenyl]-6-methyl-cyclohexyl}-propionyl)-5-methylene-5H-furan-2-one
  参考文献：
  名称：

  Total synthesis of tetronomycin

  摘要：

  The first total synthesis of (+)-tetronomycin (1), a novel tetronic acid ionophore antibiotic, has been achieved through the synthesis and assemblage of the four cyclic segments 4, 5, 7, and 8. Construction of the C5-C-13 cyclohexyl portion 5 involves as the key step either a Beckmann fragmentation of the bicyclic ketone oxime 45 or an L-Selectride-mediated reductive annulation of the nona-2,7-dienoate 53. The C-14-C28 polyether fragment 6 was constructed by a BF3-catalyzed coupling reaction of the C-14-C22 allylsilane 7 and the C23-C28 tetrahydrofuran 8 which were derived, respectively, from L-ascorbic acid or (R)-3-hydroxyisobutyrate and L-rhamnal. The union of 5 and 6 by an aldol condensation, followed by photoisomerization of the derived diastereomeric alpha,beta-unsaturated esters, provided (Z)-61, which was converted to the aldehyde 63. Subsequent acylation of the tetronate 4 with 63 via an aldol reaction-oxidation sequence afforded the protected tetronomycin 64. Final deprotection provided synthetic tetronomycin, which was characterized as its sodium salt.

  DOI：

  10.1021/jo00036a026