tert-butyl-((2S,4R)-2,4-dimethylhex-5-enyloxy)diphenylsilane | 1246843-31-1

• 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: tert-butyl-((2S,4R)-2,4-dimethylhex-5-enyloxy)diphenylsilane
• 英文别名: tert-butyl-[(2S,4R)-2,4-dimethylhex-5-enoxy]-diphenylsilane
• CAS: 1246843-31-1
• 化学式: C₂₄H₃₄OSi
• 分子量: 366.619
• InChiKey: LYBAIRCGUIWSTL-SFTDATJTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.41
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  tert-butyl-((2S,4R)-2,4-dimethylhex-5-enyloxy)diphenylsilane 在 copper(l) iodide 、 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Unexpected stereochemical tolerance for the biological activity of tyroscherin

  摘要：

  Here we describe the concise syntheses of the 15 diastereomers and key analogs of the natural product tyroscherin. While systematic analysis of the analogs clearly demonstrated that the hydrocarbon tail is important for biological activity, structure-activity relationship studies of the complete tyroscherin diastereoarray revealed a surprisingly expansive stereochemical tolerance for the cytotoxic activity. Our results represent a departure from the tenet that biological activity is constrained to a narrow pharmacophore, and highlight the recently emerging appreciation for stereochemical flexibility in defining the essential structural elements of biologically active small molecules. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2011.01.027
• 作为产物：
  描述：

  (R)-3-[(tert-butyl)diphenylsilyloxy]-1-iodo-2-methylpropane 在 正丁基锂 、 四丙基高钌酸铵 、 N-甲基吗啉氧化物 、 lithium chloride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 tert-butyl-((2S,4R)-2,4-dimethylhex-5-enyloxy)diphenylsilane
  参考文献：
  名称：

  Unexpected stereochemical tolerance for the biological activity of tyroscherin

  摘要：

  Here we describe the concise syntheses of the 15 diastereomers and key analogs of the natural product tyroscherin. While systematic analysis of the analogs clearly demonstrated that the hydrocarbon tail is important for biological activity, structure-activity relationship studies of the complete tyroscherin diastereoarray revealed a surprisingly expansive stereochemical tolerance for the cytotoxic activity. Our results represent a departure from the tenet that biological activity is constrained to a narrow pharmacophore, and highlight the recently emerging appreciation for stereochemical flexibility in defining the essential structural elements of biologically active small molecules. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2011.01.027

文献信息

• Total synthesis, stereochemical elucidation and biological evaluation of Ac₂SGL; a 1,3-methyl branched sulfoglycolipid from Mycobacterium tuberculosis
  作者：Danny Geerdink、Bjorn ter Horst、Marco Lepore、Lucia Mori、Germain Puzo、Anna K. H. Hirsch、Martine Gilleron、Gennaro de Libero、Adriaan J. Minnaard

  DOI：10.1039/c2sc21620e

  日期：——

  part of a vaccine. Here, we report the first asymmetric total synthesis of 1. Two approaches were developed for the synthesis of hydroxyphthioceranic acid (4), its polypropionate part, thereby establishing the absolute stereochemistry of the C17 hydroxyl function to be of (R)-configuration. Subsequently, 4 was regioselectively connected to the trehalose core and after selective sulfation and a final

  结核分枝杆菌（TB）的病原体结核分枝杆菌继续代表具有挑战性的病原体，导致许多人死亡。该病原体持续存在的原因是细胞包膜成分，它由长尾（糖）脂质组成，参与宿主免疫应答的调节。在细胞被膜中发现的二酰化磺基糖脂Ac 2 SGL（1）是一种有效的抗原，可刺激针对TB的免疫反应。该观察结果表明将1作为疫苗的一部分使用。在这里，我们报告的第一不对称全合成1。开发了两种方法合成羟基苯硫醚酸（4），其聚丙烯酸酯部分，从而确定C17羟基官能团的绝对立体化学为（R）-构型。随后，将4个区域选择性地连接至海藻糖核，并且在选择性硫酸化和最后的四倍脱保护步骤之后，获得纯的1。合成和天然1的身份已通过NMR和质量分析证实，此外，合成1的生物学功能与1相同，并激活了对1的最小结构修饰高度敏感的CD1b限制性和Ac 2 SGL特异性T细胞。具有相同的效力。提出了模型研究以指出1的结构特征，这些特征对于与抗原呈递分子CD1b和T细胞受体的结合很重要。
• Total Synthesis and Biological Evaluation of Tyroscherin
  作者：Hyun Seop Tae、John Hines、Ashley R. Schneekloth、Craig M. Crews

  DOI：10.1021/ol101801u

  日期：2010.10.1

  The efficient synthesis and biological evaluation of both the reported and revised structures of tyroscherin have been achieved. Central to our synthesis is a cross metathesis reaction that generated the trans-olefin regioselectively. This synthetic strategy enabled the facile manipulation of tyroscherin stereochemistry, facilitating the generation of all 16 tyroscherin diastereomers and a photoactivatable tyroscherin-based affinity probe for future mode of action studies.
• Unexpected stereochemical tolerance for the biological activity of tyroscherin
  作者：Hyun Seop Tae、John Hines、Ashley R. Schneekloth、Craig M. Crews

  DOI：10.1016/j.bmc.2011.01.027

  日期：2011.3

  Here we describe the concise syntheses of the 15 diastereomers and key analogs of the natural product tyroscherin. While systematic analysis of the analogs clearly demonstrated that the hydrocarbon tail is important for biological activity, structure-activity relationship studies of the complete tyroscherin diastereoarray revealed a surprisingly expansive stereochemical tolerance for the cytotoxic activity. Our results represent a departure from the tenet that biological activity is constrained to a narrow pharmacophore, and highlight the recently emerging appreciation for stereochemical flexibility in defining the essential structural elements of biologically active small molecules. (C) 2011 Elsevier Ltd. All rights reserved.