Name: synthesis of hypervalent iodonium alkynyl triflates for the application of generating cyanocarbenes
Uploaded: 2013-09-08T12:00:00
Description: Watch this Scientific Journal Video about Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes at JoVE.com

资助这项工程由美国化学学会石油研究基金（52488-DNI1）和北卡罗来纳大学格林斯伯勒分校深表感谢。我们还要感谢特里尼罗河博士（联合国宣传小组），以供外借我们适当的玻璃器皿这些实验。视频咨询和编辑由Aaron GLANCY也承认。

1。 HIAT苯的合成<ol><li>装备一个干燥的100毫升的圆底烧瓶中，用磁搅拌器搅拌，并有氩气气氛下的烧瓶中。钳瓶的立场，并将其放入乙腈和固体二氧化碳颗粒冷冻剂洗澡。注意：该制冷剂应为约-45℃。 </li><li>加入10毫升无水二氯甲烷中，冰冷烧瓶，并允许溶剂平衡到冷冻剂的温度。注意：在烧瓶中的过量的顶部空间是用于加入乙醚后，强制沉淀重要。 </li><li>权衡0.35克cyanophenyliodonium三氟甲磺酸?...

<ol>
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G., Kim, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Angularly+Fused+Triquinanes+from+Linear+Substrates+through+Trimethylenemethane+Diyl+[2+++3]+Cycloaddition+Reaction.">Angularly Fused Triquinanes from Linear Substrates through Trimethylenemethane Diyl [2 + 3] Cycloaddition Reaction.</a> Organic Letters. 12 (11), 2672-2674 (2010).</li><li>Beauchard, A., Phillips, V. A., Lloyd, M. D., Threadgill, M. 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高价碘炔基三氟甲磺酸酯，或HIATs，形成有可与叠氮化物源反应形成cyanocarbenes。这是非常重要的，所有必要的预防措施，因为许多在这个视频显示的试剂和中间体是可能发生爆炸和剧毒。虽然反应性的高的水平可能是危险的，如果准备不足，它表示在该播放该化合物的内在反应性可以通过捕获cyanocarbenes在各种反应如OH插入和环丙烷被利用。 其他HIATs的合成一直试图用不同的成...

有机化学的持续发展取决于新反应的设计和开发。尤其是，新的反应，使以前无法想象的合成路线的发现熊终极意义。为此目的，我们组随意转换炔的两个碳原子和一个叠氮化物的氮成cyanocarbene。1此以前未知的变换将允许在分子复杂显著增加，因为反应性cyanocarbene会迅速进一步反应。最初的努力是使用亲核炔和叠氮化物亲电的，但三唑被有效地形成在该情况下，而不是cyanocarbenes。2使用umpolung方法中，第二种方法是使用亲电炔和亲核叠氮化物和从cyanocarbene反应得到的产物是幸运的形成在该情况下，3有亲核叠氮化物的许多来源，然而，电炔烃是不太常见。本组克劳斯Banert先前报道证明了概念该反应使用炔基-氯，4但本集团与Banert组独立以及同时确定高价碘炔基三氟甲磺酸酯（HIATs）是原因好得多亲电稳定性和反应性。3,6我们这里所描述的合成，分离，和这些HIATs与叠氮化物的形成，并在原位作为cyanocarbenes反应反应。 几个安全预防措施，应继续进行这些实验之前予以考虑。一些高价碘炔基三氟甲磺酸酯是不稳定的，会发生分解，剧烈的某个时候，当暴露在空气和光线。7为了形成cyanocarbene中间，该过程需要使用叠氮化物的来源。叠氮化物是爆炸物和剧毒。8适当的个人防护装备应处理这些材料，特别是有机锡的时候可以穿，和所有操纵试剂应在适当通风罩。该cyanocarbene是一个强大的和不稳定的活性中间体。小心在小范围内开始进行实验，使氮气进化是可控的，从来没有在封闭系统中进行这些反应。如果规模化反应的需要，我们强烈建议使用安全防护罩。 先前已经发表了许多HIATs的合成被包括使用Zefirov的试剂9,10，和Koser试剂，9,11然而，这部影片将使用cyanophenyliodonium三氟甲磺酸酯试剂9,12（ 图1）。合成Cyanophenyliodonium三氟甲磺酸酯基上显示与先前报导的文献制备。与三烷基锡改性炔14 13的试剂反应，形成所需产物。后HIAT合成和分离它可以与叠氮化物反应，形成反应cyanocarbene中间（ 图2）。还有许多其他的方法可以用于合成碘炔烃，如使用炔基硅烷15和炔基硼酸酯16，但在视频的方法的原因是，在我们的经验，它有更好的效率和产率。 我们提出的机制3,5（ 图3），用于本反应包括加入叠氮化物源，以炔的β-碳，由此形成碘鎓盐的分解而碘苯和亚乙烯基碳烯。然后偏卡宾可以通过任一R-基团或酰基叠氮化物，得到炔基-叠氮化物的迁移发生的1,2 -重排。的炔基叠氮化物，然后挤出二氮以形成cyanocarbene可与衬底发生反应。应当指出，有可能是形成高价碘鎓三氟甲磺酸酯的链烯基物质的，这取决于条件。的副产品是利于在质子溶剂如碘鎓盐的质子化比重排的炔酰基叠氮化物更快更低的温度。在OH插入反应发生的另一种可能的产品是其中的偏卡宾的重排的炔基叠氮发生之前被困乙烯基醚。形成这种乙烯基醚的倾向是由R组决定。 之一的，该反应的主要优点是，卡宾反应后，将得到的腈基是一个方便的把手，进一步官能化。许多合成子可以设想用这种方法和不同的产品可以用相同的基板来形成。控制该产物混合物与温度，浓度，和R基团的炔是必要的。3含于cyanocarbenes如何表现适当的洞察，所述方法示出了一种可行的方法以快速增加化学的复杂性，以形成目标分子。如何cyanocarben的例子ë起反应包括OH插入其中的醇的亲核氧原子攻击卡宾，然后质子转移发生，二甲亚砜络合物，其中所述卡宾结合的硫原子，和环丙烷，其中卡宾反应与烯烃。

<table border="1">
<tbody>
 <tr>
 <td></td>
 <td></td>
 <td></td>
 <td>Reagent</td>
 </tr>
 <tr>
 <td>Phenyl acetylene</td>
 <td>Acros</td>
 <td>AC152461000</td>
 <td></td>
 </tr>
 <tr>
 <td>Tri-n-butyltin chloride</td>
 <td>Acros</td>
 <td>139351000</td>
 <td></td>
 </tr>
 <tr>
 <td>Lithium bis(trimethysilyl)amide</td>
 <td>Acros</td>
 <td>347701000</td>
 <td></td>
 </tr>
 <tr>
 <td>Iodobenzene diacetate</td>
 <td>Acros</td>
 <td>176560250</td>
 <td></td>
 </tr>
 <tr>
 <td>Trimethylsilyl cyanide</td>
 <td>Aldrich</td>
 <td>212849</td>
 <td>Extremely toxic. Handle this chemical only in an adequately ventilated hood with extreme caution.</td>
 </tr>
 <tr>
 <td>Trimethylsilyl triflate</td>
 <td>Alfa Aesar</td>
 <td>A12535</td>
 <td></td>
 </tr>
 <tr>
 <td>Sodium Azide</td>
 <td>Sigma-Aldrich</td>
 <td>S8032</td>
 <td>Shock sensitive.</td>
 </tr>
 <tr>
 <td>Tetrabutylammonium azide</td>
 <td>Aldrich</td>
 <td>651664</td>
 <td>If possible, store and handle in a glovebox due to this compound's hygroscopic nature.</td>
 </tr>
 <tr>
 <td>1-Heptyne</td>
 <td>Acros</td>
 <td>223460250</td>
 <td></td>
 </tr>
 <tr>
 <td>Styrene</td>
 <td>Aldrich</td>
 <td>240869</td>
 <td></td>
 </tr>
 <tr>
 <td></td>
 <td></td>
 <td></td>
 <td>[header]</td>
 </tr>
 <tr>
 <td></td>
 <td></td>
 <td></td>
 <td>Material</td>
 </tr>
 <tr>
 <td>Rotary Evaporator (Hei-VAP)</td>
 <td>Heidolph</td>
 <td>517-61000-01-0</td>
 <td></td>
 </tr>
 <tr>
 <td>Glovebox</td>
 <td>MBRAUN</td>
 <td>UL-018</td>
 <td></td>
 </tr>
 </tbody>
</table>

synthesis of hypervalent iodonium alkynyl triflates for the application of generating cyanocarbenes

在这篇文章中所描述的程序涉及的高价碘炔基三氟甲磺酸酯（HIATs）及其与叠氮化物的后续反应的合成和隔离，形成cyanocarbene中间体。的高价碘炔基三氟甲磺酸酯的合成可以是浅显的，但问题是由于隔离和反应性干。特别是，惰性气氛下使用的过滤在-45℃下一些HIATs的必要性，需要特别照顾和设备。一旦分离，所述化合物可被存储和在反应中使用的叠氮化物用于形成cyanocarbene中间体。 的证据cyanocarbene代所表现出的双氮可见挤出以及从俄亥俄州插入，亚砜络合，环丙烷化中发生的产品的特性。该cyanocarbene形成的副反应是偏二卡宾的生成，并控制该过程的条件进行了讨论。有也可能形成一个高价碘鎓三氟甲磺酸烯并进行隔离，其发电的控制手段提供。的OH插入反应包括使用HIAT，叠氮化钠或四丁基铵叠氮化物，和以甲醇为溶剂/基质。亚砜配位反应使用HIAT，叠氮化钠或四丁基铵叠氮化物，和二甲亚砜作为溶剂。该cyclopropanations可以使用或不使用溶剂来进行。叠氮化物源必须是四丁基铵叠氮化物和所示的基板是苯乙烯。

图1示出HIAT的合成通过使用cyanophenyliodonium炔基三氟甲磺酸酯。该HIAT然后可以用来产生cyanocarbenes将经环丙烷的OH插入。与苯基HIAT的OH插入反应产生2 - 甲氧基-2 - 苯基乙腈在高达75％的产率。与苯基HIAT环丙烷反应生成1,2 - diphenylcyclopropanecarbonitrile在多达61％的产量。尽管在视频没有证明，二甲亚砜络合物可以与二甲亚砜进行反应，以产生DMSO-加合物在27％的产率，当与cyanocarbene中间发生...

Watch this Scientific Journal Video about Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes at JoVE.com

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes

本文中所描述的合成，分离，和超价碘炔基三氟甲磺酸酯（HIATs）反应，用叠氮化物，以产生cyanocarbenes。该程序将涉及空气敏感和制冷剂的技术，包括在惰性气氛下冷过滤。处理的合成的化合物及安全性也将被讨论。

高价碘鎓炔基三氟甲磺酸酯的生成Cyanocarbenes的合成应用

The procedures described in this article involve the synthesis and isolation of hypervalent iodonium alkynyl triflates (HIATs) and their subsequent ...

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Maleimide-bearing bifunctional probes have been employed for decades for the site-selective modification of thiols in biomolecules, especially antibodies. ...

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides

功能化单有机硼化合物共轭法高效合成全碳第四纪中心

The conjugate addition of organometallic reagents to &#945;,&#946;-unsaturated carbonyls represents an important method to generate C&#8211;C bonds in the ...