6-Benzyloxy-6-methyl-heptanethioic acid S-tert-butyl ester | 203719-03-3

• 分子结构分类: 有机化合物
• 英文名称: 6-Benzyloxy-6-methyl-heptanethioic acid S-tert-butyl ester
• 英文别名: S-tert-butyl 6-methyl-6-phenylmethoxyheptanethioate
• CAS: 203719-03-3
• 化学式: C₁₉H₃₀O₂S
• 分子量: 322.512
• InChiKey: NUTPHYNFAZGPIL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  22
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6-Benzyloxy-6-methyl-heptanethioic acid S-tert-butyl ester 在 palladium on activated charcoal 四氢吡咯 、 4-二甲氨基吡啶 、 palladium diacetate 、 potassium fluoride 、 三丁基膦 、 2,6-二叔丁基-4-甲基苯酚 、 氢气 、 二异丁基氢化铝 、 三乙基硼氢化锂 、 对甲苯磺酸 、 三乙胺 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醇 、 二氯甲烷 为溶剂， 反应 108.5h， 生成 rac-(6R^*)-2-methyl-6-[(4R^*,7aR^*)-7a-methyl-4-(phenylthio)octahydroinden-1-yl]heptan-2-ol
  参考文献：
  名称：

  Total Synthesis of 25-Hydroxy Vitamin D₃ Northern Portion, Involving Tandem Conjugate Additions

  摘要：

  New approaches to 25-hydroxy vitamin D building blocks 7 and 8 have been developed. Tandem acid-catalyzed conjugate addition of ketene acetal 2d or 2c and acceptors 3 and then 11 yielded 5b (76% from 3) or 22 (64%), respectively, with the proper relative configuration on C20, C17, and C13 (steroid numbering, all compounds are racemic). The trans-hydrindan ring junction in 16 and 27 has been secured by chirality transfer in palladium-catalyzed hydrogenolysis of formates 15 and 26. Treatment of 16 with N-bromoacetamide followed by NaOH yielded a mixture of 8 beta,9 beta- and 8 alpha,9 alpha-epoxides 18 in a ratio of ca. 2:1, which was tosylated and reduced with lithium aluminum hydride without separation. The required diol 20 and its isomer 21 were obtained. In a complementary approach, 27 was oxidized into 8 alpha,9 alpha-epoxide 29 with a new reagent composed of m-CPBA, KF, and 2,6-di-tert-butyl-4-methylphenol. Opening of the epoxide ring in 29 with thiophenoxide anion followed by oxidation afforded dihydroxy sulfone 31. The latter was reduced via the respective dimesylate, and then the protective benzyloxy group was removed yielding 8.

  DOI：

  10.1021/jo971967x
• 作为产物：
  描述：

  叔丁基硫醇 、 Potassium; 6-benzyloxy-6-methyl-heptanoate 在 草酰氯 、 三乙胺 作用下， 生成 6-Benzyloxy-6-methyl-heptanethioic acid S-tert-butyl ester
  参考文献：
  名称：

  Total Synthesis of 25-Hydroxy Vitamin D₃ Northern Portion, Involving Tandem Conjugate Additions

  摘要：

  New approaches to 25-hydroxy vitamin D building blocks 7 and 8 have been developed. Tandem acid-catalyzed conjugate addition of ketene acetal 2d or 2c and acceptors 3 and then 11 yielded 5b (76% from 3) or 22 (64%), respectively, with the proper relative configuration on C20, C17, and C13 (steroid numbering, all compounds are racemic). The trans-hydrindan ring junction in 16 and 27 has been secured by chirality transfer in palladium-catalyzed hydrogenolysis of formates 15 and 26. Treatment of 16 with N-bromoacetamide followed by NaOH yielded a mixture of 8 beta,9 beta- and 8 alpha,9 alpha-epoxides 18 in a ratio of ca. 2:1, which was tosylated and reduced with lithium aluminum hydride without separation. The required diol 20 and its isomer 21 were obtained. In a complementary approach, 27 was oxidized into 8 alpha,9 alpha-epoxide 29 with a new reagent composed of m-CPBA, KF, and 2,6-di-tert-butyl-4-methylphenol. Opening of the epoxide ring in 29 with thiophenoxide anion followed by oxidation afforded dihydroxy sulfone 31. The latter was reduced via the respective dimesylate, and then the protective benzyloxy group was removed yielding 8.

  DOI：

  10.1021/jo971967x