(2R,3S)-2-methyl-5-phenylmethoxy-3-triethylsilyloxypentanal | 158574-42-6

• 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: (2R,3S)-2-methyl-5-phenylmethoxy-3-triethylsilyloxypentanal
• CAS: 158574-42-6
• 化学式: C₁₉H₃₂O₃Si
• 分子量: 336.547
• InChiKey: HFMSPZKVESWJNU-HKUYNNGSSA-N

物化性质

• 沸点：
  401.5±45.0 °C(predicted)
• 密度：
  0.960±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.82
• 重原子数：
  23
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3S)-2-methyl-5-phenylmethoxy-3-triethylsilyloxypentanal 在 吡啶 、 2,6-二甲基吡啶 、 甲酸 、 乙醚 、 氯代二环己基硼烷 、 四丁基氟化铵 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 8.0h， 生成 [(2R,3R,5R,7R,8R,9S)-7-[tert-butyl(dimethyl)silyl]oxy-2-[(1S)-2-[(4S,5S,6R)-6-[(2R)-1-[tert-butyl(dimethyl)silyl]oxypropan-2-yl]-2,2,5-trimethyl-1,3-dioxan-4-yl]-1-methoxyethyl]-4,4,8-trimethyl-9-(2-phenylmethoxyethyl)-1,10-dioxaspiro[4.5]decan-3-yl] bis(2-trimethylsilylethyl) phosphate
  参考文献：
  名称：

  Tanimoto, Norihiko; Gerritz, Samuel W.; Sawabe, Akiyoshi, Angewandte Chemie, 1994, vol. 106, # 6, p. 674 - 677

  摘要：

  DOI：
• 作为产物：
  描述：

  3-苄氧基丙醛 在 咪唑 、 三氟甲磺酸二丁硼 、 三甲基铝 、 二异丁基氢化铝 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.58h， 生成 (2R,3S)-2-methyl-5-phenylmethoxy-3-triethylsilyloxypentanal
  参考文献：
  名称：

  Aplyronine A, a Potent Antitumor Substance of Marine Origin, Aplyronines B and C, and Artificial Analogues:  Total Synthesis and Structure−Cytotoxicity Relationships

  摘要：

  The enantioselective total synthesis of aplyronine A (1), a potent antitumor substance of marine origin, was achieved by a convergent-approach Three segments 4, 5, and 6, corresponding to the C5-C11, C21-C27, and C28-C34 portions of aplyronine A (1), were prepared using:the Evans aldol reaction and the Sharpless epoxidation as key steps. The coupling reaction of 4 with iodide 7 followed by julia olefination with sulfone 8 gave the C5-C20 segment 9, while the julia coupling reaction between segments 5 and 6 provided the C21-C34 segment 10. Julia olefination between segments 9 and 10 and the subsequent four-carbon homologation reaction led to seco acid 83, which was converted into aplyronine A (1) by Yamaguchi lactonization followed by the introduction of two amino acids. The use of the [(3,4-dimethoxybenzyl)oxy]methyl group as a protecting group for the hydroxyl at C29 was crucial for this synthesis. The enantioselective synthesis of two natural congeners, aplyronines B (2) acid C (3), was also carried out using the intermediates for the synthesis of 1, which determined the absolute stereostructures of 2 and 3 unambiguously. To study the structure-cytotoxicity relationships of aplyronines, artificial analogues of 1 were synthesized and their cytotoxicities were evaluated: the trimethylserine moiety, two hydroxyl groups, and the side-chain portion in 1 turned out to be important in the potent cytotoxicity shown by 1. Biological studies with aplyronine A (1) showed that 1 inhibited polymerization of G-actin to F-actin and depolymerized F-actin to G-actin.

  DOI：

  10.1021/jo9606113

文献信息

• Development of a novel inducer of protein–protein interactions based on aplyronine A
  作者：Takayuki Ohyoshi、Atsuhiro Takano、Mayu Namiki、Tomotaka Ogura、Yuto Miyazaki、Yuta Ebihara、Koichi Takeno、Ichiro Hayakawa、Hideo Kigoshi

  DOI：10.1039/c8cc04613a

  日期：——

  An aplyronine A–swinholide A hybrid, consisting of the macrolactone part of aplyronine A and the side chain part of swinholide A, was designed, synthesized, and evaluated for biological activities.

  一个由aplyronine A的大环内酯部分和swinholide A的侧链部分组成的混合物被设计、合成并用于生物活性评估。
• Structure–activity relationship studies on an antitumor marine macrolide using aplyronine a–swinholide A hybrid
  作者：Takayuki Ohyoshi、Atsuhiro Takano、Imari Kikuchi、Tomotaka Ogura、Mayu Namiki、Yuto Miyazaki、Takahiro Hirano、Shota Konishi、Yuta Ebihara、Koichi Takeno、Ichiro Hayakawa、Hideo Kigoshi

  DOI：10.1039/d2ob00118g

  日期：——

  An aplyronine A–swinholide A hybrid, consisting of the macrolactone part of aplyronine A and the side chain part of swinholide A, was designed, synthesized, and biologically evaluated. This hybrid induced protein–protein interactions between two major cytoskeletal proteins actin and tubulin in the same manner as aplyronine A, and exhibited potent cytotoxicity and actin-depolymerizing activity. The

  设计、合成和生物学评估了由 alyronine A 的大环内酯部分和 swinholide A 的侧链部分组成的 alyronine A-swinholide A 杂化物。这种杂合体以与 alyronine A 相同的方式诱导两种主要细胞骨架蛋白肌动蛋白和微管蛋白之间的蛋白质相互作用，并表现出强大的细胞毒性和肌动蛋白解聚活性。N、N、O中甲氧基的重要性-三甲基丝氨酸酯通过使用杂合类似物的氨基酸部分的构效关系研究得到澄清。此外，比较 alyronine A 和 swinholide A 的侧链类似物的肌动蛋白解聚活性表明，swinholide A 的侧链类似物的肌动蛋白解聚活性比 alyronine A 弱得多。
• Aplyronine A, a Potent Antitumor Substance of Marine Origin, Aplyronines B and C, and Artificial Analogues:  Total Synthesis and Structure−Cytotoxicity Relationships
  作者：Hideo Kigoshi、Kiyotake Suenaga、Tsuyoshi Mutou、Takeshi Ishigaki、Toshiyuki Atsumi、Hiroyuki Ishiwata、Akira Sakakura、Takeshi Ogawa、Makoto Ojika、Kiyoyuki Yamada

  DOI：10.1021/jo9606113

  日期：1996.1.1

  The enantioselective total synthesis of aplyronine A (1), a potent antitumor substance of marine origin, was achieved by a convergent-approach Three segments 4, 5, and 6, corresponding to the C5-C11, C21-C27, and C28-C34 portions of aplyronine A (1), were prepared using:the Evans aldol reaction and the Sharpless epoxidation as key steps. The coupling reaction of 4 with iodide 7 followed by julia olefination with sulfone 8 gave the C5-C20 segment 9, while the julia coupling reaction between segments 5 and 6 provided the C21-C34 segment 10. Julia olefination between segments 9 and 10 and the subsequent four-carbon homologation reaction led to seco acid 83, which was converted into aplyronine A (1) by Yamaguchi lactonization followed by the introduction of two amino acids. The use of the [(3,4-dimethoxybenzyl)oxy]methyl group as a protecting group for the hydroxyl at C29 was crucial for this synthesis. The enantioselective synthesis of two natural congeners, aplyronines B (2) acid C (3), was also carried out using the intermediates for the synthesis of 1, which determined the absolute stereostructures of 2 and 3 unambiguously. To study the structure-cytotoxicity relationships of aplyronines, artificial analogues of 1 were synthesized and their cytotoxicities were evaluated: the trimethylserine moiety, two hydroxyl groups, and the side-chain portion in 1 turned out to be important in the potent cytotoxicity shown by 1. Biological studies with aplyronine A (1) showed that 1 inhibited polymerization of G-actin to F-actin and depolymerized F-actin to G-actin.
• Tanimoto, Norihiko; Gerritz, Samuel W.; Sawabe, Akiyoshi, Angewandte Chemie, 1994, vol. 106, # 6, p. 674 - 677
  作者：Tanimoto, Norihiko、Gerritz, Samuel W.、Sawabe, Akiyoshi、Noda, Takeshi、Filla, Sandra A.、Masamune, Satoru

  DOI：——

  日期：——