(3R,4R,5R)-5-[(4R,5S,6R,9R)-9-[tert-butyl(dimethyl)silyl]oxy-6-hydroxy-4-methyl-5-phenylmethoxyundeca-1,7-diynyl]-3-methyl-4-phenylmethoxyoxolan-2-one | 1333067-53-0

• 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: (3R,4R,5R)-5-[(4R,5S,6R,9R)-9-[tert-butyl(dimethyl)silyl]oxy-6-hydroxy-4-methyl-5-phenylmethoxyundeca-1,7-diynyl]-3-methyl-4-phenylmethoxyoxolan-2-one
• CAS: 1333067-53-0
• 化学式: C₃₇H₅₀O₆Si
• 分子量: 618.886
• InChiKey: GQZGFMBZPUUMCW-BCGKRAQFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.91
• 重原子数：
  44
• 可旋转键数：
  13
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  74.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (3R,4R,5R)-5-[(4R,5S,6R,9R)-9-[tert-butyl(dimethyl)silyl]oxy-6-hydroxy-4-methyl-5-phenylmethoxyundeca-1,7-diynyl]-3-methyl-4-phenylmethoxyoxolan-2-one 在 2,6-二甲基吡啶 、 四氧化锇 、 2,4,6-三氯苯甲酰氯 、 三乙胺 、 三氟乙酸 、 柠檬酸 作用下， 以 乙醚 、 二氯甲烷 、 水 、 溶剂黄146 、 甲苯 、 叔丁醇 为溶剂， 反应 20.08h， 生成
  参考文献：
  名称：

  Direct Entry to Erythronolides via a Cyclic Bis[Allene]

  摘要：

  The complexity and low tractability of antibiotic macrolides pose serious challenges to addressing the problem of resistance through semi- or total synthesis. Here we describe a new strategy involving the preparation of a complex yet tractable macrocycle and the transformation of this macrocycle into a range of erythronolide congeners. These compounds represent valuable sectors of erythromycinoid structure space and constitute intermediates with the potential to provide further purchase in this space. The routes are short. The erythronolides were prepared in three or fewer steps from the macrocycle, which was prepared in a longest linear sequence of 11 steps.

  DOI：

  10.1021/ja207496p
• 作为产物：
  描述：

  (S)-4-benzyl-3-((2S,3S)-3-(benzyloxy)-4,4-dimethoxy-2-methylbutanoyl)oxazolidin-2-one 在 三乙烯二胺 、 锂硼氢 、 正丁基锂 、 三氟乙酸 、 zinc dibromide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 水 、 溶剂黄146 、 二甲基亚砜 为溶剂， 反应 23.0h， 生成 (3R,4R,5R)-5-[(4R,5S,6R,9R)-9-[tert-butyl(dimethyl)silyl]oxy-6-hydroxy-4-methyl-5-phenylmethoxyundeca-1,7-diynyl]-3-methyl-4-phenylmethoxyoxolan-2-one
  参考文献：
  名称：

  Direct Entry to Erythronolides via a Cyclic Bis[Allene]

  摘要：

  The complexity and low tractability of antibiotic macrolides pose serious challenges to addressing the problem of resistance through semi- or total synthesis. Here we describe a new strategy involving the preparation of a complex yet tractable macrocycle and the transformation of this macrocycle into a range of erythronolide congeners. These compounds represent valuable sectors of erythromycinoid structure space and constitute intermediates with the potential to provide further purchase in this space. The routes are short. The erythronolides were prepared in three or fewer steps from the macrocycle, which was prepared in a longest linear sequence of 11 steps.

  DOI：

  10.1021/ja207496p

文献信息

• Direct Entry to 4,10-Didesmethyl (9<i>S</i>)-Dihydroerythronolide A via Catalytic Allene Osmylation
  作者：Libing Yu、Huan Wang、Novruz G. Akhmedov、Christopher Sowa、Kai Liu、Hiyun Kim、Lawrence Williams

  DOI：10.1021/acs.orglett.6b01151

  日期：2016.6.17

  to 4,10-didesmethyl (9S)-dihydroerythronolide A (1) from known cyclic bis[allene] 13 is reported. Key structural and mechanistic aspects of the synthesis are discussed along with catalytic allene osmylation. An improved route to 13 is also described.

  脱甲基赤藓醇内酯已成为大环内酯的靶标，可证明对耐药菌有效。据报道，从已知的环状双[丙二烯] 13到4,10-二甲基（9 S）-二氢赤藓醇内酯A（1）的五步序列。讨论了合成的关键结构和机理，以及催化的烯丙糖基化。还描述了一种改进的到达13的途径。