(E)-(R)-8-(tert-Butyl-dimethyl-silanyloxy)-7-hydroxy-4-methyl-oct-2-enoic acid methyl ester | 125010-99-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (E)-(R)-8-(tert-Butyl-dimethyl-silanyloxy)-7-hydroxy-4-methyl-oct-2-enoic acid methyl ester
• CAS: 125010-99-3
• 化学式: C₁₆H₃₂O₄Si
• 分子量: 316.513
• InChiKey: YDXNTADIVCTUMV-ARLHGKGLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.51
• 重原子数：
  21.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  55.76
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (E)-(R)-8-(tert-Butyl-dimethyl-silanyloxy)-7-hydroxy-4-methyl-oct-2-enoic acid methyl ester 在 4-二甲氨基吡啶 、 氢氧化钾 、 氯化亚砜 、 草酰氯 、 三氟化硼乙醚 、 potassium tert-butylate 、 四丁基氟化铵 、 水 、 二异丁基氢化铝 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 丙酮 为溶剂， 反应 18.67h， 生成 2,2-Dimethyl-propionic acid 2-((2R,3S,6R)-6-{(E)-3-[(2R,5S)-5-((R)-1-hydroxy-ethyl)-tetrahydro-furan-2-yl]-propenyl}-3-methyl-tetrahydro-pyran-2-yl)-ethyl ester
  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：

  (4S,5R)-3-<(R)-5,6-(Isopropylidenedioxy)hexanoyl>-4-methyl-5-phenyl-1,3-oxazolidin-2-one 在 咪唑 、 盐酸 、 lithium hydroxide 、 水 、 双氧水 、 sodium hexamethyldisilazane 、 二异丁基氢化铝 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 、 乙腈 为溶剂， 反应 22.0h， 生成 (E)-(R)-8-(tert-Butyl-dimethyl-silanyloxy)-7-hydroxy-4-methyl-oct-2-enoic acid methyl ester
  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