(2R,3R,4R,5S)-5-(tert-Butyl-dimethyl-silanyloxy)-3-(2-methoxy-ethoxymethoxy)-2,4,6-trimethyl-hept-6-enal | 86535-04-8

• 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: (2R,3R,4R,5S)-5-(tert-Butyl-dimethyl-silanyloxy)-3-(2-methoxy-ethoxymethoxy)-2,4,6-trimethyl-hept-6-enal
• CAS: 86535-04-8
• 化学式: C₂₀H₄₀O₅Si
• 分子量: 388.62
• InChiKey: MEBBIRDMTVVXBK-OKYOBFRVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.43
• 重原子数：
  26.0
• 可旋转键数：
  13.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (2R,3R,4R,5S)-5-(tert-Butyl-dimethyl-silanyloxy)-3-(2-methoxy-ethoxymethoxy)-2,4,6-trimethyl-hept-6-enal 在 2-chloro-1,3,2-dithioborolane 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 tert-Butyl-{(S)-1-[(R)-1-((4S,5S,6R)-5,6-dimethyl-[1,3]dioxan-4-yl)-ethyl]-2-methyl-allyloxy}-dimethyl-silane
  参考文献：
  名称：

  Studies in Macrolide Synthesis: A Stereocontrolled Synthesis of Oleandolide Employing Reagent- and Substrate-Controlled Aldol Reactions of (S)-1-(Benzyloxy)-2-methylpentan-3-one

  摘要：

  A highly stereocontrolled total synthesis of oleandolide (2), the aglycon of the macrolide antibiotic oleandomycin (1), has been completed in 8% overall yield (20 steps longest Linear sequence, 26 steps in total) with 90% overall diastereoselectivity. Initially, reagent-controlled syn aldol reactions of (S)-1-(benzyloxy)-2-methylpentan-3-one ((S)-8) were employed to prepare adducts 6 (SS) and 7 (SA), which were elaborated to provide the two advanced fragments 33 and 27, respectively. Coupling of these fragments followed by functional group manipulation and macrolactonization gave the macrocyclic ketone 42, possessing S configuration at C-9. Elaboration of 42 to oleandolide, however, proved troublesome. Substrate-controlled syn and anti aldol reactions of ketone (S)-8, meanwhile, provided the adducts 6 (SS) and 7 (AA), which enabled synthesis, via fragments 64 and 60, of the key macrocyclic ketone intermediate 69, having R configuration at C-9. Stereoselective epoxidation of ketone 69, by reaction with dimethylsulfonium methylide under macrocyclic stereocontrol, provided the (8R)-epoxide 83; subsequent elaboration then gave oleandolide (2).

  DOI：

  10.1021/ja00104a010
• 作为产物：
  描述：

  (2S,3R,4S)-5-Benzyloxymethoxy-3-(tert-butyl-dimethyl-silanyloxy)-2,4-dimethyl-pentanal 在 palladium on activated charcoal P(C₄H₉)3 、 氢气 、 双氧水 、 二异丁基氢化铝 、 pyridinium chlorochromate 、 methyloxirane 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 42.0h， 生成 (2R,3R,4R,5S)-5-(tert-Butyl-dimethyl-silanyloxy)-3-(2-methoxy-ethoxymethoxy)-2,4,6-trimethyl-hept-6-enal
  参考文献：
  名称：

  大环内酯合成的研究：oleandomycin和lankamycin的两个手性片段的合成。

  摘要：

  描述了夹竹桃霉素和兰卡霉素的两个结构相关的手性片段C 1 -C 7和C 8 -C 13的合成。

  DOI：

  10.1016/s0040-4039(00)81643-3