(2S,3S,4S,5R,6S)-7-hydroxy-3,5-(isopropylidenedioxy)-2,4,6-trimethylheptyl p-toluenesulfonate | 86534-97-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,3S,4S,5R,6S)-7-hydroxy-3,5-(isopropylidenedioxy)-2,4,6-trimethylheptyl p-toluenesulfonate
• 英文别名: [(2S)-2-[(4S,5S,6R)-6-[(2S)-1-hydroxypropan-2-yl]-2,2,5-trimethyl-1,3-dioxan-4-yl]propyl] 4-methylbenzenesulfonate
• CAS: 86534-97-6
• 化学式: C₂₀H₃₂O₆S
• 分子量: 400.536
• InChiKey: XRFNIAOWEHSWBD-FYAJOAKPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.12
• 重原子数：
  27.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  82.06
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (2S,3S,4S,5R,6S)-7-hydroxy-3,5-(isopropylidenedioxy)-2,4,6-trimethylheptyl p-toluenesulfonate 在 sodium periodate 、 W-2 Raney Ni 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 24.0h， 生成 (2S,3R,4R,5S,6S,8RS,9S,10R,11S,12S,13R)-13-<(benzyloxy)methoxy>-9,11-bis(tert-butyldimethylsiloxy)-3,5-(isopropylidenedioxy)-2,4,6,10,12-pentamethyltetradecane-1,8-diol
  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：

  Toluene-4-sulfonic acid (S)-2-{(4S,5S,6R)-6-[(S)-2-(tert-butyl-dimethyl-silanyloxy)-1-methyl-ethyl]-2,2,5-trimethyl-[1,3]dioxan-4-yl}-propyl ester 在 四丁基氟化铵 作用下， 生成 (2S,3S,4S,5R,6S)-7-hydroxy-3,5-(isopropylidenedioxy)-2,4,6-trimethylheptyl p-toluenesulfonate
  参考文献：
  名称：

  Stereoselective synthesis of .gamma.,.delta.-epoxy-.beta.-methyl-.gamma.-(trimethylsilyl)alkanols. Synthesis of the C(1)-C(7) segment of 6-deoxyerythronolide B

  摘要：

  DOI：

  10.1021/ja00305a045

文献信息

• Studies in macrolide synthesis: a synthesis of two chiral fragments of oleandomycin and lankamycin.
  作者：Ian Peterson

  DOI：10.1016/s0040-4039(00)81643-3

  日期：1983.1

  A synthesis of the two structurally-related chiral fragments, C1-C7 and C8-C13, of oleandomycin and lankamycin in described.

  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。
• Studies in macrolide synthesis: A stereocontrolled synthesis of a (9S)-macrolide intermediate for oleandomycin using chiral boron reagents.
  作者：Ian Paterson、M.Anne Lister、Roger D. Norcross

  DOI：10.1016/s0040-4039(00)91728-3

  日期：1992.3

  The (9S)-macrolide 1 (P = TBS) was prepared in 14 steps (5% yield) with 63% overall ds starting from the ethyl ketone (S)-2. The C1-C7 and C8-C13 segments, 3 and 4, were obtained via boron enolate aldol reactions mediated by (+)- and (-)-(Ipc)2BOTf, respectively.