(2S,4R)-5-(3-(benzyloxy)-5-bromo-2-methoxyphenyl)-1-((tert-butyldimethylsilyl)oxy)-4-methylpentan-2-ol | 1601460-57-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (2S,4R)-5-(3-(benzyloxy)-5-bromo-2-methoxyphenyl)-1-((tert-butyldimethylsilyl)oxy)-4-methylpentan-2-ol
• CAS: 1601460-57-4
• 化学式: C₂₆H₃₉BrO₄Si
• 分子量: 523.583
• InChiKey: GDHSUJUYCALQPJ-XXBNENTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.99
• 重原子数：
  32.0
• 可旋转键数：
  11.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  47.92
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (2S,4R)-5-(3-(benzyloxy)-5-bromo-2-methoxyphenyl)-1-((tert-butyldimethylsilyl)oxy)-4-methylpentan-2-ol 在 吡啶 、 草酰氯 、 三氟化硼乙醚 、 1,8-双二甲氨基萘 、 氟化氢吡啶 、 二甲基亚砜 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 13.5h， 生成 (6S,8R)-9-(3-(benzyloxy)-5-bromo-2-methoxyphenyl)-6-methoxy-4,8-dimethylnon-2-yn-5-ol
  参考文献：
  名称：

  Total synthesis of reblastatin: convenient preparation of coupling partners and scaled assembly

  摘要：

  Potentially scalable total synthesis of reblastatin was achieved based on Panek's previous study. Novel and convenient synthetic routes were developed for the known C8-C20 and C1-C7 coupling partners. The challenging C8-C20 fragment was prepared from TBS protected (S)-5-(hydroxymethyl)dihydrofuran-2(3H)-one (6) in nine steps (20% overall yield), and the C1-C7 fragment was synthesized from commercially available 3,4,6-tri-O-acetyl-D-glucal (9) in eight steps (35% overall yield). On a larger scale, Panek's eight-step assembly of the target molecule from the two partners was also slightly modified, giving 45 mg reblastatin (19% overall yield) in the first batch synthesis. Notable feature of our study is the settlement of the C14 chirality through a diastereoselective alpha-alkylation of 6 followed by a three-step full reduction of the lactone carboxyl, making vastly available 6 a universally applicable C11-C14 synthon for benzenoid/benzoquinone ansamycins. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.03.020
• 作为产物：
  描述：

  (3R,5S)-3-(3-(benzyloxy)-5-bromo-2-methoxybenzyl)-5-(((tert-butyldimethylsilyl)oxy)methyl)dihydrofuran-2(3H)-one 在 二异丁基氢化铝 、 儿萘酚硼烷 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 反应 32.25h， 生成 (2S,4R)-5-(3-(benzyloxy)-5-bromo-2-methoxyphenyl)-1-((tert-butyldimethylsilyl)oxy)-4-methylpentan-2-ol
  参考文献：
  名称：

  Total synthesis of reblastatin: convenient preparation of coupling partners and scaled assembly

  摘要：

  Potentially scalable total synthesis of reblastatin was achieved based on Panek's previous study. Novel and convenient synthetic routes were developed for the known C8-C20 and C1-C7 coupling partners. The challenging C8-C20 fragment was prepared from TBS protected (S)-5-(hydroxymethyl)dihydrofuran-2(3H)-one (6) in nine steps (20% overall yield), and the C1-C7 fragment was synthesized from commercially available 3,4,6-tri-O-acetyl-D-glucal (9) in eight steps (35% overall yield). On a larger scale, Panek's eight-step assembly of the target molecule from the two partners was also slightly modified, giving 45 mg reblastatin (19% overall yield) in the first batch synthesis. Notable feature of our study is the settlement of the C14 chirality through a diastereoselective alpha-alkylation of 6 followed by a three-step full reduction of the lactone carboxyl, making vastly available 6 a universally applicable C11-C14 synthon for benzenoid/benzoquinone ansamycins. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.03.020