(1Z)-1-iodo-3-(tert-butyldimethylsilyloxy)-1-propene | 151502-81-7

• 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: (1Z)-1-iodo-3-(tert-butyldimethylsilyloxy)-1-propene
• 英文别名: cis-3-dimethyl(1,1-dimethylethyl)silyloxy-1-iodo-1-propene；(Z)-1-tert-butyldimethylsilyloxy-3-iodo-2-propene；(Z)-3-(tert-butyldimethylsilyl)oxy-1-iodo-1-propene；(Z)-tert-butyl((3-iodoallyl)oxy)dimethylsilane；tert-butyl-[(Z)-3-iodoprop-2-enoxy]-dimethylsilane
• CAS: 151502-81-7
• 化学式: C₉H₁₉IOSi
• 分子量: 298.239
• InChiKey: ONOBORLJYLLBRF-SREVYHEPSA-N

物化性质

• 沸点：
  239.2±23.0 °C(Predicted)
• 密度：
  1.287±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.96
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 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：

  (1Z)-1-iodo-3-(tert-butyldimethylsilyloxy)-1-propene 在 甲醇 、 四(三苯基膦)钯 、 正丁基锂 、 potassium carbonate 、 magnesium 、 zinc(II) chloride 作用下， 反应 8.75h， 生成 methyl cis-9-(tert-butyldimethylsiloxy)-7-nonen-2-ynoate
  参考文献：
  名称：

  Pd-Catalyzed Cycloisomerization to 1,2- Dialkylidenecycloalkanes. 1

  摘要：

  Enhancing synthetic efficiency requires the development of synthetic reactions that, to the extent possible, are simple additions wherein everything else is required only in catalytic amounts. The Alder ene reaction constitutes a classical reaction that meets this requirement that has much unrealized potential. A transition-metal-catalyzed version helps to increase that potential by permitting this reaction to proceed under mild conditions. A significant benefit of transition metal catalysis is the feasibility of diverting the reaction along pathways not feasible under thermal conditions. The synthesis of 1,3-dienes rather than 1,4-dienes is a very important diversion because of the utility of 1,3-dienes as reaction partners in the Diels-Alder reaction, another highly atom economical process. A catalyst derived from palladium acetate cycloisomerizes 1,6- and 1,7-enynes to dialkylidenecyclopentanes and -cyclohexanes. 1,3-Diene formation is favored over the Alder ene process by both steric and electronic effects. The reaction is highly chemoselective-tolerating a wide diversity of functionality including hydroxyl groups, ketones, esters, alkynyl and enol ethers, alkynyl and vinyl silanes, and enones. Many of the substrates are available by palladium-catalyzed alkylation reactions-highlighting the effectiveness of palladium catalyzed methodology in organic synthesis. The atom-economical nature of these reactions combined with the Diels-Alder reaction permit butadiene and dimethyl propargylmalonate to be molded into a polyhydro-as-indacene. The mechanism of this reaction may involve a tautomerization of an enyne-Pd(+2) complex to a pallada(+4)cyclopentene intermediate as a key step.

  DOI：

  10.1021/ja00089a015
• 作为产物：
  描述：

  叔丁基二甲基(2-丙炔氧基)硅烷 在 吗啉 、 碘 、 potassium diazodicarboxylate 作用下， 以 吡啶 、 甲醇 、 溶剂黄146 、 苯 为溶剂， 反应 48.0h， 生成 (1Z)-1-iodo-3-(tert-butyldimethylsilyloxy)-1-propene
  参考文献：
  名称：

  糖乙炔通过二钴六羰基配合物的一步式回收形成中等醚环

  摘要：

  将四个C-1炔基化D-葡萄糖转化为相应的二钴六羰基配合物。在用酸处理后将它们全部再循环以形成中等大小的（7、8、9和10元）醚环。关键机制是与二钴六羰基配合物连接的烯丙基阳离子的顺反双键异构化。通过使用铑催化剂，在高压加氢下成功实现了分解。

  DOI：

  10.1016/s0040-4020(98)00013-1

文献信息

• Palladium-catalysed regio- and stereoselective arylative substitution of γ,δ-epoxy-α,β-unsaturated esters and amides by sodium tetraaryl borates
  作者：Yasemin Bilgi、Melih Kuş、Levent Artok

  DOI：10.1039/d0ob01226b

  日期：——

  Palladium-catalysed reactions of γ,δ-epoxy-α,β-unsaturated esters and amides with NaBAr4 reagents proceeded regio- and stereoselectively, producing allylic homoallyl alcohols with aryl-substituents in the allylic position for a wide range of substrates. AsPh3 was found to be a competent ligand for the arylation reaction, whereas phosphine ligand/Lewis acidic organoboron combinations favoured the substitution

  钯催化的 γ,δ-环氧-α,β-不饱和酯和酰胺与 NaBAr 4试剂的反应以区域选择性和立体选择性进行，产生在烯丙基位置具有芳基取代基的烯丙基高烯丙基醇，适用于各种底物。AsPh 3被发现是芳基化反应的有效配体，而膦配体/Lewis 酸性有机硼组合有利于氧亲核试剂（例如H 2 O、ROH）的取代反应。
• Asymmetric synthesis of Pachastrissamine (Jaspine B) and its diastereomers viaη3-allylpalladium intermediates
  作者：Mikko Passiniemi、Ari M. P. Koskinen

  DOI：10.1039/c0ob00643b

  日期：——

  A short route for the synthesis of Pachastrissamine (Jaspine B), an anhydrosphingosine derivative, and all three of its diastereomers is presented. The route consists of only 9 steps from the commercially available Garner's aldehyde. The furan framework is formed via an η3-allylpalladium intermediate.

  合成以下物质的捷径 Pachastrissamine （茉莉花B），脱水鞘氨醇衍生物及其所有三个非对映异构体。该路线仅由市售Garner醛中的9个步骤组成。呋喃框架形成经由一个η 3 π-烯丙基中间体。
• The Simultaneous In-Situ Generation of Aldehydes and Phosphorus Ylides: A Convenient Multi-Step One-Pot Olefination Protocol
  作者：Qian Wang、Heng-xu Wei、Manfred Schlosser

  DOI：10.1002/(sici)1099-0690(199912)1999:12<3263::aid-ejoc3263>3.0.co;2-u

  日期：1999.12

  nucleophilic addn. of an organolithium reagent to DMF are basic enough to deprotonate alkyltriphenylphosphonium salts suspended in THF. The aldehydes, liberated by the spontaneous decompn. of the resulting a-amino alcs. (hemi-aminals), undergo a Wittig reaction with the simultaneously generated P ylides to afford olefins in excellent overall yields. This in situ method offers the unique advantage in

  Li a-(二甲氨基)醇盐由亲核加成物产生。有机锂试剂对 DMF 的碱性足以使悬浮在 THF 中的烷基三苯基鏻盐去质子化。醛，由自发分解释放。产生的α-氨基醇。（半缩醛胺），与同时生成的 P 叶立德进行 Wittig 反应，以优异的总产率提供烯烃。这种原位方法在其适用于不稳定醛方面提供了独特的优势，否则这些醛将成为 (Z/E)-异构化或自缩合过程的牺牲品。[在 SciFinder (R) 上]
• Synthesis of Enantiomerically Purecis-Cyclopropylboronic Esters
  作者：Joachim E. A. Luithle、Jörg Pietruszka

  DOI：10.1002/1099-0690(200007)2000:14<2557::aid-ejoc2557>3.0.co;2-i

  日期：2000.7

  Highly stable, enantiomerically pure cyclopropylboronic esters are desirable building blocks for the preparation of a plethora of different cyclopropane derivatives. Whereas trans-configured compounds proved to be readily available, we herein report the first synthesis of the corresponding cis-cyclopropanes. The scope and limitation of this process will be discussed. The absolute configuration of the

  高度稳定的对映体纯环丙基硼酸酯是制备大量不同环丙烷衍生物的理想结构单元。虽然反式构型化合物被证明是容易获得的，但我们在此报告了相应顺式环丙烷的首次合成。将讨论此过程的范围和限制。产品的绝对构型可以通过化学和光谱相关来确定。
• Regioselective <i>trans</i> ‐Hydrostannation of Boron‐Capped Alkynes
  作者：Romain Melot、Tomas J. Saiegh、Alois Fürstner

  DOI：10.1002/chem.202101901

  日期：2021.12.6

  periphery of the loaded ruthenium catalyst is the likely cause for the excellent regioselectivity observed in the hydrostannation of bench-stable alkynyl-B(aam) derivatives (aam=anthranilamido). The reaction follows a stereochemically unorthodox trans-addition mode and delivers highly versatile gem-dimetalated alkene building blocks for synthesis.

  外围：负载钌催化剂外围的氢键阵列可能是在稳定的炔基-B(aam) 衍生物（aam=蒽酰胺）的氢化锡化过程中观察到优异区域选择性的原因。该反应遵循立体化学非正统的反式加成模式，并提供用于合成的高度通用的宝石二金属化烯烃结构单元。