(4S,5R)-5-(tert-butyldiphenylsiloxy)-4-methylhexanal | 175613-30-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (4S,5R)-5-(tert-butyldiphenylsiloxy)-4-methylhexanal
• 英文别名: (4S,5R)-5-[tert-butyl(diphenyl)silyl]oxy-4-methylhexanal
• CAS: 175613-30-6
• 化学式: C₂₃H₃₂O₂Si
• 分子量: 368.591
• InChiKey: CPTSECJAVCFYIP-VQTJNVASSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.57
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4S,5R)-5-(tert-butyldiphenylsiloxy)-4-methylhexanal 在 正丁基锂 、 三丁基膦 、 三氟甲磺酸 、 三氟化硼乙醚 、 potassium tert-butylate 、 臭氧 、 (+)-B-methoxydiisocamphenylborane 作用下， 以 乙醚 为溶剂， 反应 1.83h， 生成 (2S,3S,6S,7R)-7-[tert-butyl(diphenyl)silyl]oxy-3-[(4-methoxyphenyl)methoxy]-2,6-dimethyloctanal
  参考文献：
  名称：

  Synthesis of the C1−C21 Fragment of the Serine/Threonine Phosphatase Inhibitor Tautomycin

  摘要：

  Compound 40 containing the C-1-C-21 region of tautomycin has been synthesized. The two halves (4 and 5) of this spirocyclic section were each constructed using Matteson's chloromethylene insertion reaction. Cr/Ni-mediated coupling of compounds 4 and 5 resulted in a structure containing the C-1-C-21 section of tautomycin. Oxidation of the resultant allylic alcohol to the ketone and removal of the alpha,beta unsaturation yielded compound 39. Treatment with DDQ removed both PMB protecting groups and allowed the spirocyclic ketal to form producing compound 40, ready for further extension to the natural product tautomycin.

  DOI：

  10.1021/jo952083l
• 作为产物：
  描述：

  (5S,6R)-6-(hydroxy)-5-methyl-1-heptene 在 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 三丁基膦 、 臭氧 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.08h， 生成 (4S,5R)-5-(tert-butyldiphenylsiloxy)-4-methylhexanal
  参考文献：
  名称：

  Synthesis of the C1−C21 Fragment of the Serine/Threonine Phosphatase Inhibitor Tautomycin

  摘要：

  Compound 40 containing the C-1-C-21 region of tautomycin has been synthesized. The two halves (4 and 5) of this spirocyclic section were each constructed using Matteson's chloromethylene insertion reaction. Cr/Ni-mediated coupling of compounds 4 and 5 resulted in a structure containing the C-1-C-21 section of tautomycin. Oxidation of the resultant allylic alcohol to the ketone and removal of the alpha,beta unsaturation yielded compound 39. Treatment with DDQ removed both PMB protecting groups and allowed the spirocyclic ketal to form producing compound 40, ready for further extension to the natural product tautomycin.

  DOI：

  10.1021/jo952083l

文献信息

• Total Synthesis of (±)-Oxacyclododecindione
  作者：Kevin Seipp、Vincent Grölz、Hagen Glass、Elisabeth Quraishi、Nina Vierengel、Till Opatz

  DOI：10.1021/acs.joc.4c00333

  日期：2024.4.19

  Racemic total synthesis of the natural product oxacyclododecindione, isolated in 2008 as the first member of the oxacyclododecindione family, is reported. Studies toward this molecule commenced with a biomimetic late-stage C–H oxidation starting from 14-deoxyoxacyclododecindione as a known precursor. This provided insights into the reactivity of the macrolactone class but did not permit the synthesis

  据报道，天然产物 oxacyclododecindione 的外消旋全合成于 2008 年分离，是 oxacyclododecindione 家族的第一个成员。对该分子的研究始于 14-脱氧环十二烷二酮作为已知前体的仿生晚期 C-H 氧化。这提供了对大内酯类反应性的见解，但不允许合成目标天然产物。基于这些结果，设想了一种通过分子内 Friedel-Crafts 酰化结合 Barton 脱羧引入叔醇的合成策略，这是以前合成工作中的一个主要挑战。这导致了 （±）-氧氧环十二烷二酮的 11 步外消旋全合成，该合成以其强大的抗炎和抗纤维化活性而闻名。
• Synthesis of the C1−C21 Fragment of the Serine/Threonine Phosphatase Inhibitor Tautomycin
  作者：Karl W. Maurer、Robert W. Armstrong

  DOI：10.1021/jo952083l

  日期：1996.1.1

  Compound 40 containing the C-1-C-21 region of tautomycin has been synthesized. The two halves (4 and 5) of this spirocyclic section were each constructed using Matteson's chloromethylene insertion reaction. Cr/Ni-mediated coupling of compounds 4 and 5 resulted in a structure containing the C-1-C-21 section of tautomycin. Oxidation of the resultant allylic alcohol to the ketone and removal of the alpha,beta unsaturation yielded compound 39. Treatment with DDQ removed both PMB protecting groups and allowed the spirocyclic ketal to form producing compound 40, ready for further extension to the natural product tautomycin.