(E)-1-iodo-6-<(tert-butyldimethylsilyl)oxy>-1-hexene | 132260-33-4

• 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: (E)-1-iodo-6-<(tert-butyldimethylsilyl)oxy>-1-hexene
• 英文别名: (E)-tert-butyl((6-iodohex-5-en-1-yl)oxy)dimethylsilane；(E)-6-(tert-Butyldimethylsilyloxy)-1-iodohex-1-ene；tert-butyl-((E)-6-iodohex-5-enyloxy)dimethylsilane；(E)-1-iodo-6-[(tert-butyldimethylsilyl)oxy]-1-hexene；tert-butyl-[(E)-6-iodohex-5-enoxy]-dimethylsilane
• CAS: 132260-33-4
• 化学式: C₁₂H₂₅IOSi
• 分子量: 340.32
• InChiKey: UBMZBNVXQKHURM-CSKARUKUSA-N

物化性质

• 沸点：
  294.5±33.0 °C(Predicted)
• 密度：
  1.210±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.13
• 重原子数：
  15
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  (E)-1-iodo-6-<(tert-butyldimethylsilyl)oxy>-1-hexene 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 216.0h， 生成 玉米烯酮
  参考文献：
  名称：

  Synthesis of .beta.-resorcylic macrolides via organopalladium chemistry. Application to the total synthesis of (S)-zearalenone

  摘要：

  The beta-resorcylic macrolides are a class of naturally occurring 12- and 14-membered macrolides. Zearalenone (1), a 14-membered macrolide of this type, displays useful biological activity, which has led to great synthetic interest. In this paper the intramolecular coupling reaction of an organostannane with an electrophile is used to construct beta-resorcylic macrolides. The intramolecular coupling of an aryl iodide with a vinylstannane provided the highest yield of lactones. This methodology was then used to prepare (S)-zearalenone (1).

  DOI：

  10.1021/jo00008a053
• 作为产物：
  描述：

  5-己炔-1-醇 在 4-二甲氨基吡啶 、 N-碘代丁二酰亚胺 、 Schwartz's reagent 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 96.5h， 生成 (E)-1-iodo-6-<(tert-butyldimethylsilyl)oxy>-1-hexene
  参考文献：
  名称：

  Synthesis of .beta.-resorcylic macrolides via organopalladium chemistry. Application to the total synthesis of (S)-zearalenone

  摘要：

  The beta-resorcylic macrolides are a class of naturally occurring 12- and 14-membered macrolides. Zearalenone (1), a 14-membered macrolide of this type, displays useful biological activity, which has led to great synthetic interest. In this paper the intramolecular coupling reaction of an organostannane with an electrophile is used to construct beta-resorcylic macrolides. The intramolecular coupling of an aryl iodide with a vinylstannane provided the highest yield of lactones. This methodology was then used to prepare (S)-zearalenone (1).

  DOI：

  10.1021/jo00008a053

文献信息

• Bis(oxazoline) and Bis(oxazolinyl)pyridine Copper Complexes as Enantioselective Diels−Alder Catalysts:  Reaction Scope and Synthetic Applications
  作者：David A. Evans、David M. Barnes、Jeffrey S. Johnson、Thomas Lectka、Peter von Matt、Scott J. Miller、Jerry A. Murry、Roger D. Norcross、Eileen A. Shaughnessy、Kevin R. Campos

  DOI：10.1021/ja991191c

  日期：1999.8.1

  the use of this chiral catalyst in more complex Diels−Alder processes, are described. Similarly, the cationic copper complex 9a, [Cu((S,S)-t-Bu-pybox)](SbF6)2, is effective in the Diels−Alder reactions of monodentate acrolein dienophiles while the closely related complex, 9d [Cu((S,S)-Bn-pybox)](SbF6)2, is the preferred Lewis acid catalyst for acrylate dienophiles in reactions with cyclopentadiene.

  已经研究了由双（恶唑啉）铜配合物催化的 Diels-Alder 反应的范围。特别是，[Cu((S,S)-t-Bu-box)](SbF6)2 (1b) 已被证明可以催化 3-propenoyl-2-oxazolidinone (2) 和一系列的 Diels-Alder 反应。具有高对映选择性的取代二烯。这种阳离子复合物也已成功用于类似分子内过程的催化。描述了 ent-Δ1-四氢大麻酚、ent-莽草酸和 isopulo'upone 的全合成，其特点是在更复杂的 Diels-Alder 过程中使用这种手性催化剂。类似地，阳离子铜配合物 9a，[Cu((S,S)-t-Bu-pybox)](SbF6)2，在单齿丙烯醛亲二烯体的 Diels-Alder 反应中是有效的，而密切相关的配合物 9d [Cu ((S,S)-Bn-pybox)](SbF6)2,
• Stereoselective Csp ³ −Csp ² Cross‐Couplings of Chiral Secondary Alkylzinc Reagents with Alkenyl and Aryl Halides
  作者：Juri Skotnitzki、Alexander Kremsmair、Daniel Keefer、Ye Gong、Regina Vivie‐Riedle、Paul Knochel

  DOI：10.1002/anie.201910397

  日期：2020.1.2

  We report palladium-catalyzed cross-coupling reactions of chiral secondary non-stabilized dialkylzinc reagents, prepared from readily available chiral secondary alkyl iodides, with alkenyl and aryl halides. This method provides α-chiral alkenes and arenes with very high retention of configuration (dr up to 98:2) and satisfactory overall yields (up to 76 % for 3 reaction steps). The configurational stability

  我们报告了手性仲非稳定的二烷基锌试剂的钯催化交叉偶联反应，该试剂由易于获得的手性仲烷基碘与烯基和芳基卤化物制备。该方法提供的α-手性烯烃和芳烃具有很高的构型保留率（dr高达98：2）和令人满意的总收率（3个反应步骤高达76％）。确定了这些手性不稳定的二烷基锌试剂的构型稳定性，并在25°C下超过了数小时。进行DFT计算以合理化催化循环中的立体保留。此外，在绝对立体化学的控制下，交叉偶联反应用于倍半萜（S）-和（R）-姜黄素的有效全合成中。
• Enantioselective Aza-Heck Cyclizations of <i>N</i>-(Tosyloxy)carbamates: Synthesis of Pyrrolidines and Piperidines
  作者：Xiaofeng Ma、Ian R. Hazelden、Thomas Langer、Rachel H. Munday、John F. Bower

  DOI：10.1021/jacs.8b12689

  日期：2019.2.27

  Pd(0)-systems modified with SPINOL-derived phosphoramidate ligands promote highly enantioselective aza-Heck cyclizations of alkenyl N-(tosyloxy)carbamates. The method provides versatile access to challenging N-heterocycles and represents the broadest scope enantioselective aza-Heck protocol developed to date.

  用 SPINOL 衍生的氨基磷酸酯配体修饰的 Pd(0)-系统促进烯基 N-（甲苯磺酰氧基）氨基甲酸酯的高度对映选择性 aza-Heck 环化。该方法提供了对具有挑战性的 N-杂环的通用访问，并代表了迄今为止开发的最广泛的对映选择性 aza-Heck 协议。
• BZM055, an Iodinated Radiotracer Candidate for PET and SPECT Imaging of Myelin and FTY720 Brain Distribution
  作者：Emmanuelle Briard、David Orain、Christian Beerli、Andreas Billich、Markus Streiff、Marc Bigaud、Yves P. Auberson

  DOI：10.1002/cmdc.201000477

  日期：2011.4.4

  as a surrogate tracer to study its pharmacokinetics and organ distribution in patients and, given that FTY720 accumulates in myelin sheaths, for myelin imaging. BZM055 (2 a, 2‐iodo‐FTY720) can be easily radiolabeled with 123I (for SPECT) or 124I (for PET). Not only does it closely mimic the pharmacokinetics and organ distribution of FTY720, but also its affinity, selectivity for S1P receptors, phosphorylation

  FTY720（芬戈莫德，Gilenya®）是一种鞘氨醇1-磷酸（S1P）受体调节剂，在多发性硬化症患者口服后显示出显着的治疗功效。由于FTY720不包含其PET或SPECT放射性同位素的半衰期与其药代动力学性质兼容的任何原子，因此不能直接用于成像。相反，我们建议使用BZM055作为替代示踪剂，以研究其在患者中的药代动力学和器官分布，并考虑到FTY720积累在髓鞘中，用于髓鞘成像。BZM055（2 a，2- iodo -FTY720）可以轻松地用123 I（用于SPECT）或124进行放射性标记我（用于PET）。它不仅紧密模拟了FTY720的药代动力学和器官分布，而且还紧密模拟了FTY720的亲和力，对S1P受体的选择性，磷酸化动力学以及整体理化特性。[ 123 I] BZM055目前正在开发用于临床成像。
• Intramolecular Nitroalkene Diels-Alder Reaction Catalyzed by Brønsted Acids
  作者：Norito Takenaka、Andreina Aguado

  DOI：10.1055/s-0030-1260542

  日期：2011.6

  Bronsted acid catalysis of intramolecular Diels―Alder cyclizations of (E)-1-nitro-1,6,8-nonatrienes and (E)-1-nitro-1,7,9-decatrienes was investigated. Catalyzed reactions showed significantly higher endo selectivities than the corresponding thermal reactions. To our knowledge, this is the first example of catalysis (substoichiometric amount of catalysts) of the intramolecular nitroalkene Diels―Alder

  分子内狄尔斯的布朗斯台德酸催化——研究了 (E)-1-硝基-1,6,8-壬三烯和 (E)-1-硝基-1,7,9-癸三烯的阿尔德环化反应。催化反应显示出比相应的热反应显着更高的内向选择性。据我们所知，这是分子内硝基烯烃 Diels-Alder 反应催化（亚化学计量的催化剂量）的第一个例子。