(4S,4aR,5S,8aR)-4,5-Dimethyl-3-oxoperhydroisochroman | 142560-66-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (4S,4aR,5S,8aR)-4,5-Dimethyl-3-oxoperhydroisochroman
• 英文别名: (4S,4aR,5S,8aR)-4,5-dimethyl-1,4,4a,5,6,7,8,8a-octahydroisochromen-3-one
• CAS: 142560-66-5
• 化学式: C₁₁H₁₈O₂
• 分子量: 182.263
• InChiKey: LIKHFWOJSCBNGS-XKNYDFJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  5-<(tert-Butyldiphenylsilyl)oxy>-4-methylpentanal 在 草酰氯 、 氢氟酸 、 L-Selectride 、 二甲基亚砜 、 三乙胺 、 红铝 、 叔丁醇 作用下， 以 四氢呋喃 、 甲苯 、 乙腈 、 苯 为溶剂， 反应 32.5h， 生成 (4S,4aR,5S,8aR)-4,5-Dimethyl-3-oxoperhydroisochroman
  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