(1E,3S,5S)-3-t-butyldimethylsilyloxy-1-iodo-5-methylnonene | 83009-48-7

• 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: (1E,3S,5S)-3-t-butyldimethylsilyloxy-1-iodo-5-methylnonene
• 英文别名: (3S,5S,E)-3-(tert-Butyldimethylsiloxy)-1-iodo-5-methylnon-1-ene；(3S,5S,E)-3-t-butyldimethylsilyloxy-1-iodo-5-methyl-1-nonene；tert-butyl-[(E,3S,5S)-1-iodo-5-methylnon-1-en-3-yl]oxy-dimethylsilane
• CAS: 83009-48-7
• 化学式: C₁₆H₃₃IOSi
• 分子量: 396.427
• InChiKey: QFBSVKRPHXZAED-AMXOMPAFSA-N

物化性质

• 沸点：
  352.3±25.0 °C(Predicted)
• 密度：
  1.139±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.54
• 重原子数：
  19
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  (1E,3S,5S)-3-t-butyldimethylsilyloxy-1-iodo-5-methylnonene 在 氢氟酸 、 叔丁基锂 、 苯硫酚铜(I) 、 三(二甲胺基)膦 作用下， 以 乙腈 为溶剂， 生成 (E)-6-[(2S,3R)-3-Hydroxy-2-((E)-(3S,5S)-3-hydroxy-5-methyl-non-1-enyl)-5-oxo-cyclopentylsulfanyl]-hex-2-enoic acid methyl ester
  参考文献：
  名称：

  Synthesis of 7-thiaprostaglandin E1 congeners: Potent inhibitors of platelet aggregation.

  摘要：

  合成了一系列新型的7-硫前列腺素E1衍生物和同系物，采用一步法的三组分耦合过程，该过程涉及向(R)-4-叔丁基二甲基硅氧基-2-环戊烯酮引入α侧链（硫醇）和β侧链（有机铜试剂）。还通过酶法或化学方法制备了几种7-硫前列腺素E1的酸衍生物。这些产物的立体化学基于对手性保护的环戊烯酮和手性ω侧链的结果进行分配。发现某些7-硫前列腺素E1同系物的血小板聚集抑制活性比PGE1更强。文中讨论了这些同系物的结构-活性关系。

  DOI：

  10.1248/cpb.33.2359
• 作为产物：
  描述：

  (E)-1-iodo-5-methylnon-1-en-3-one 在 咪唑 、 (-)-(S)-BINAL-H 作用下， 反应 5.0h， 生成 (1E,3S,5S)-3-t-butyldimethylsilyloxy-1-iodo-5-methylnonene
  参考文献：
  名称：

  Synthesis of 7-thiaprostaglandin E1 congeners: Potent inhibitors of platelet aggregation.

  摘要：

  合成了一系列新型的7-硫前列腺素E1衍生物和同系物，采用一步法的三组分耦合过程，该过程涉及向(R)-4-叔丁基二甲基硅氧基-2-环戊烯酮引入α侧链（硫醇）和β侧链（有机铜试剂）。还通过酶法或化学方法制备了几种7-硫前列腺素E1的酸衍生物。这些产物的立体化学基于对手性保护的环戊烯酮和手性ω侧链的结果进行分配。发现某些7-硫前列腺素E1同系物的血小板聚集抑制活性比PGE1更强。文中讨论了这些同系物的结构-活性关系。

  DOI：

  10.1248/cpb.33.2359

文献信息

• Synthesis of 7-Fluoro-2,4-methylene-17,20-dimethylprostacyclins. Novel stable prostacyclin analogs as potent anti-anginal agents
  作者：Yasushi Matsumura、Toyomichi Shimada、Toshiaki Nakayama、Masahiro Urushihara、Tomoyuki Asai、Yoshitomi Morizawa、Arata Yasuda

  DOI：10.1016/0040-4020(95)00468-n

  日期：1995.8

  Synthesis of new stable fluoroprostacyclins, 7-fluoro-2,4-methylene-17, 20-dimethylprostacyclins (1,2) with potent and long-lasting anti-anginal activities has been achieved. The cyclobutylene prostaglandin skeleton 10 was constructed efficiently according to three-component coupling reaction. Stereospecific fluorination of silyl ether 11 and subsequent cyclization of the fluoride 12 successfully provided

  已经合成了具有有效和持久的抗心绞痛活性的新的稳定的氟代前列环素，7-氟-2,4-亚甲基-17、20-二甲基前列环素（1,2）。根据三组分偶联反应，有效地构建了环丁烯前列腺素骨架10。甲硅烷基醚11的立体定向氟化和氟化物12的随后环化成功提供了所需的7-氟-2,4-亚甲基-17,20-二甲基前列环素。
• Nitro-olefin trapping reaction of enolates generated by conjugate addition reaction: short syntheses of PGE1, 6-Oxo-PGE1, 6-Oxo-PGF1α, and PGI2
  作者：Toshio Tanaka、Atsuo Hazato、Kiyoshi Bannai、Noriaki Okamura、Satoshi Sugiura、Kenji Manabe、Takeshi Toru、Seizi Kurozumi、Masaaki Suzuki、Toshio Kawagishi、Ryoji Noyori

  DOI：10.1016/s0040-4020(01)90018-3

  日期：1987.1

  in situ generated by conjugate addition of organocopper reagents to the chiral oxygenated cyclopentenone synthon, R-4, gives the three-component coupling products in a regiospecific manner. The intermediary nitronate anion 17 is further transformed into the nitro compound or 6-oxo-PGE1 (19) in a single pot. This coupling reaction is applicable to syntheses of naturally occurring prostaglandins such

  通过将有机铜试剂共轭添加到手性含氧环戊烯酮合成子R-4中，原位生成的烯醇化物被硝基烯烃捕获，从而以区域特异性方式生成三组分偶联产物。在单个罐中将中间体亚硝酸根阴离子17进一步转化为硝基化合物或6-氧代-PGE 1（19）。该偶联反应是适用于天然存在的前列腺素如PGE的合成1，6-氧代PGF 1α，和PGI 2。
• Synthesis of the key component for preparation of 6-ketoprostaglandins by a two-component coupling process: synthesis of 6-keto-prostaglandin E₁, ornoprostil and Δ²-trans-6-ketoprostaglandin E₁
  作者：Yasufumi Kawanaka、Naoya Ono、Yukio Yoshida、Sentaro Okamoto、Fumie Sato

  DOI：10.1039/p19960000715

  日期：——

  Starting with commercially available (3S,4R)-3-(methoxymethyloxy)-2-methylidene-4- siloxycyclopentanone-2, useful 6-keto-prostaglandin intermediates 1 have been prepared in good yields by a sequence of reactions which includes treatment with NaBr in the presence of BF3 . OEt(2), Pd-catalysed coupling of the resulting 2-bromomethyl-4-siloxycyclopent-2-enone 3 with the alkenylborane 4 or 9 and conversion of the alkenyl moiety into an epoxy and then into a keto group. The synthesis of 6-keto-PGE(1), ornoprostil and Delta(2)-trans-6-keto-PGE(1) by using 1 is also described.
• Synthesis of new stable fluoroprostacyclin analogs with potent anti-anginal activity
  作者：Tomoyuki Asai、Yoshitomi Morizawa、Toyomichi Shimada、Toshiaki Nakayama、Masahiro Urushihara、Yasushi Matsumura、Arata Yasuda

  DOI：10.1016/0040-4039(94)02217-y

  日期：1995.1

  Synthesis of new stable fluoroprostacyclins, 7-fluoro-2,4-methylene-17,20-dimethylprostacyclins (1, 2) with potent and long-lasting anti-anginal activities has been achieved via three-component coupling reaction and stereospecific fluorination.
• Design and synthesis of a selective EP4-Receptor agonist. Part 1: discovery of 3,7-DithiaPGE1 derivatives and identification of Their ω chains
  作者：Toru Maruyama、Masaki Asada、Tai Shiraishi、Hiromu Egashira、Hideyuki Yoshida、Takayuki Maruyama、Shuichi Ohuchida、Hisao Nakai、Kigen Kondo、Masaaki Toda

  DOI：10.1016/s0968-0896(01)00351-0

  日期：2002.4

  Improvement of EP4-receptor selectivity and the agonist activity by introduction of heteroatoms into the a chain of PGE(1) was investigated. Among the compounds tested, 3,7-dithiaPGE(1) 4a exhibited good EP4-receptor selectivity and agonist activity. Further modification of the omega chain of 3,7-dithiaPGE(1) was performed to improve EP4-receptor selectivity and agonist activity. Of the compounds produced, 16-phenyl-omega-tetranor-3.7-dithiaPGE(1) 4p possessing moderate EP4-receptor selectivity and agonist activity. was identified as a new chemical lead for further optimization by modification of the aromatic moiety. (C) 2002 Elsevier Science Ltd. All rights reserved.