ethyl (Z)-5-(tert-butyldiphenylsilyloxy)-2-fluoropent-2-enoate | 918667-14-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl (Z)-5-(tert-butyldiphenylsilyloxy)-2-fluoropent-2-enoate
• 英文别名: ethyl (Z)-5-[tert-butyl(diphenyl)silyl]oxy-2-fluoropent-2-enoate
• CAS: 918667-14-8
• 化学式: C₂₃H₂₉FO₃Si
• 分子量: 400.565
• InChiKey: HXMZSTQYXRKXSJ-FXBPSFAMSA-N

物化性质

• 沸点：
  445.9±45.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.37
• 重原子数：
  28
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl (Z)-5-(tert-butyldiphenylsilyloxy)-2-fluoropent-2-enoate 在 titanium(IV) tetraethanolate 、 lithium aluminium tetrahydride 、 2-碘酰基苯甲酸 作用下， 以 四氢呋喃 、 乙酸乙酯 为溶剂， 反应 7.83h， 生成 (S)-N-(Z)-5-([tert-butyl(diphenyl)silyl]oxy)-2-fluoro-2-pentenylidene-2-methyl-2-propanesulfinamide
  参考文献：
  名称：

  氟化假肽的合成：在非对映选择性地将有机金属试剂添加到N-（叔丁烷亚磺酰基）-α-氟代亚胺中的金属介导的立体化学逆转†

  摘要：

  研究了有机金属试剂与N-（叔丁烷亚磺酰基）-α-氟亚胺的加成反应。根据有机金属种类（格利雅试剂或锌酸盐络合物）的性质，我们能够以高到高非对映体比率控制新建立的立体异构中心的构型。手性β-氟代烯丙基胺是合成带有肽键模拟物的含氟烯烃部分的氟化假肽的关键合成子。

  DOI：

  10.1039/c0ob00773k
• 作为产物：
  描述：

  methyl 3-((tert-butyldiphenylsilyl)oxy)propanoate 在 sodium hydroxide 、 sodium tetrahydroborate 、 正丁基锂 、 草酰氯 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 23.0h， 生成 ethyl (Z)-5-(tert-butyldiphenylsilyloxy)-2-fluoropent-2-enoate
  参考文献：
  名称：

  Tandem reduction–olefination of triethyl 2-acyl-2-fluoro-2-phosphonoacetates and a synthetic approach to Cbz-Gly-Ψ[(Z)-CFC]-Gly dipeptide isostere

  摘要：

  (Z)-alpha-Fluoro-alpha,beta-unsaturated esters (Z)-7a-f were stereoselectively prepared by a tandem reduction-olefination of triethyl 2-acyl-2-fluoro-2-phosphonoacetates 6a-f with NaBH4 in EtOH. A concise synthesis of Cbz-Gly-Psi[(Z)-CF=C]-Gly (26) as a dipeptide isostere was achieved via the tandem reduction-olefination of the corresponding 2-acyl-2-fluoro-2-phosphonoacetate 20. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.09.096

文献信息

• Fluorinated Pseudopeptide Analogues of the Neuropeptide 26RFa: Synthesis, Biological, and Structural Studies
  作者：Camille Pierry、Samuel Couve-Bonnaire、Laure Guilhaudis、Cindy Neveu、Amélie Marotte、Benjamin Lefranc、Dominique Cahard、Isabelle Ségalas-Milazzo、Jérôme Leprince、Xavier Pannecoucke

  DOI：10.1002/cbic.201300325

  日期：2013.9.2

  Fluoro‐olefin in place of a peptide: Dipeptides analogues containing a fluoro‐olefin moiety in place of the peptide bond have been synthesized and introduced into the bioactive C‐terminal heptapeptide of the neuropeptide 26RFa by SPPS. The fluoro‐olefin moiety is an effective mimic of the peptide bond that enhances peptide stability, has little impact on its conformation and slightly better bioactivity

  氟代烯烃代替肽：含有氟代烯烃部分代替肽键的二肽类似物已经合成，并通过SPPS引入到神经肽26RFa的生物活性C端七肽中。氟代烯烃部分是肽键的有效模拟物，可增强肽的稳定性，对其构象影响很小，生物活性稍强。
• Diastereocontrolled addition of organometallic reagents to S-chiral N-(tert-butanesulfinyl)-α-fluoroenimines
  作者：Camille Pierry、Ludivine Zoute、Philippe Jubault、Emmanuel Pfund、Thierry Lequeux、Dominique Cahard、Samuel Couve-Bonnaire、Xavier Pannecoucke

  DOI：10.1016/j.tetlet.2008.10.140

  日期：2009.1

  Grignard and organolithium reagents efficiently react with (S)-N-(tert-butanesulfinyl)-α-fluoroenimines to provide chiral allylamines in excellent yields and with diastereomeric ratios of up to 96:4. Acidic removal of the sulfinyl group and simple functional group transformations allow to get enantiopure fluoroolefin dipeptide mimics.

  格氏试剂和有机锂试剂可与（S）-N-（叔丁烷亚磺酰基）-α-氟亚胺类有效地反应，以优异的收率和高达96：4的非对映体比率提供手性烯丙胺。酸性除去亚磺酰基和简单的官能团转化可得到对映体纯的氟烯烃二肽模拟物。
• Efficient Synthesis of Fluoroalkenes via Diethylzinc-Promoted Wittig Reaction
  作者：Philippe Jubault、Xavier Pannecoucke、Ludivine Zoute、Guillaume Dutheuil、Jean-Charles Quirion

  DOI：10.1055/s-2006-950208

  日期：2006.10

  The synthesis of α-fluoroacrylates and α-bromo-α-fluoroalkenes was achieved in very good yields using aldehydes and ketones, triphenylphosphine, diethylzinc as promoter, and ethyl dibromofluoroacetate or dibromofluoromethane, respectively. A change in the addition sequence was critical in order to obtain exclusively α-fluoroacrylates in good yields.

  α-氟丙烯酸酯和α-溴-α-氟烯烃的合成得到了非常好的产率，使用了醛和酮、三苯基磷、二乙基锌作为促进剂，以及乙基二溴氟乙酸酯或二溴氟甲烷。改变添加顺序对独占性获得α-氟丙烯酸酯的高产率至关重要。
• Diethylzinc-Mediated One-Step Stereoselective Synthesis of α-Fluoroacrylates from Aldehydes and Ketones. Two Different Pathways Depending on the Carbonyl Partner
  作者：G. Lemonnier、L. Zoute、G. Dupas、J.-C. Quirion、P. Jubault

  DOI：10.1021/jo900422m

  日期：2009.6.5

  A efficient methodology allowing the one-pot stereoselective synthesis of alpha-fluoroacrylates, based on the addition of ethyl dibromofluoroacetate to a carbonyl derivative using diethylzinc as organometallic mediator, is described. Two different pathways have been identified depending on the involved carbonyl partner. In the case of aldehydes, an E2-type mechanism has been identified, whereas ketones go through an E1cb-type mechanism.
• Tandem reduction–olefination of triethyl 2-acyl-2-fluoro-2-phosphonoacetates and a synthetic approach to Cbz-Gly-Ψ[(Z)-CFC]-Gly dipeptide isostere
  作者：Shigeki Sano、Yoko Kuroda、Katsuyuki Saito、Yukiko Ose、Yoshimitsu Nagao

  DOI：10.1016/j.tet.2006.09.096

  日期：2006.12

  (Z)-alpha-Fluoro-alpha,beta-unsaturated esters (Z)-7a-f were stereoselectively prepared by a tandem reduction-olefination of triethyl 2-acyl-2-fluoro-2-phosphonoacetates 6a-f with NaBH4 in EtOH. A concise synthesis of Cbz-Gly-Psi[(Z)-CF=C]-Gly (26) as a dipeptide isostere was achieved via the tandem reduction-olefination of the corresponding 2-acyl-2-fluoro-2-phosphonoacetate 20. (c) 2006 Elsevier Ltd. All rights reserved.