Name: one-pot microwave-assisted conversion of anomeric nitrate-esters to trichloroacetimidates
Uploaded: 2018-01-15T13:00:00
Description: Watch this Scientific Journal Video about One-pot Microwave-assisted Conversion of Anomeric Nitrate-esters to Trichloroacetimidates at JoVE.com

作者要感谢范德比尔特大学和化学生物学研究所的资助。Mr. 伯克利埃利斯和 Prof. 是公认的高分辨率质谱分析。

1. 有代表性的微波辅助脱硝
<ol><li>将叠硝酸酯 (1.0 equiv, 0.2 摩尔) 放在8毫升的微波反应瓶中。反应的规模可以增加到几个摩尔, 而不会对反应进展产生任何不利影响。</li>
	<li>将叠-硝酸酯溶于20% 蒽醌丙酮 (0.1 米, 2.0 毫升)。将吡啶 (5.0 equiv, 0.08 毫升, 1.0 摩尔) 加入反应釜。将该反应容器盖在微波反应器腔内, 并将其置于微波炉辐照瓶中。</li>
	<li>照射解决方案在120° c 为15分钟, 搅拌和固定保持时间?...

<ol>
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本教程中描述的协议提供了一种将硝酸酯转化为有用的、无功功能的方法。从更广泛的意义上说, 使用微波反应器来完成碳水化合物合成过程中的特定动作, 有可能使困难的转变变得轻便和例行。在本教程中, 我们的目标是演示如何在微波照射的情况下处理碳水化合物。
在父母反应的情况下, 以前的努力, 以实现脱硝通常依赖于强亲核试剂和延长反应时间。本文所描述的技术的?...

由于它们在分子生物学中无处不在, 碳水化合物一直是化学合成的长期目标。1,2,3在任何成功的合成运动的核心是正确部署糖基化反应, 以建立低聚糖链。4,5,6,7,8,9,10,11,12不奇怪的是, 有大量的方法来安装糖苷债券。13,14汤姆·柯尼希斯-克诺尔方法是已知最早的程序之一, 它涉及将糖氯化物或溴化物与酒精成分结合, 通常在重金属 (汞或银) 活化作用下。15相关的糖氟化物在1981年被醛集团首次作为捐赠者引入, 并因其热化学稳定性的提高而得到广泛应用。在反应谱的相反端的16是糖化, 它比其他卤化物的反应要多得多。增加的反应性伴随着增加的 stereocontrol, 特别是当形成α连接的寡糖。17除了 "haloglycosides" 外, thioglycosides 还发现了广泛的效用, 部分原因在于它们易于形成, 稳定性对大量的反应条件和活化亲试剂。18
上述方法的重点是将 anomeric 醇转化为 "氧", 即由受体分子中的酒精激活并最终取代的潜离组。Anomeric 氧活化, 如施密特学派所描述的, 重点是将 C1 氧本身转化为一个离群。19这种方法是最强大的, 广泛应用于化学糖基化反应。Trichloroacetimidate 捐赠者从还原糖和乙容易地准备, 在基地存在例如碳酸钾 (K2CO3) 或 18-环 [5.4. 0] undec-7-烯 (DBU)。这些物种, 然后激活使用刘易斯酸。20
最近, 我们报告说, 2-叠-1-trichloroacetimidate 捐助者可以直接从 glycals 的准备。这一过程涉及两个反应, 一锅程序从 2-叠-1-硝酸酯。21此详细的协议旨在帮助从业者成功完成高产转化。特别感兴趣的是该序列的第一步, 它着重于微波辅助加热下的热脱硝。我们也希望提供一个直观的教程, 在有机合成中使用微波反应器。

<table>
	<tbody>
		<tr>
			<td>230 400 mesh silica gel</td>
			<td>SiliCycle Inc</td>
			<td>R10030B</td>
			<td></td>
		</tr>
		<tr>
			<td>TLC plates</td>
			<td>SiliCycle Inc</td>
			<td>TLG-R10014B-527</td>
			<td></td>
		</tr>
		<tr>
			<td>Ceric ammonium molybdate</td>
			<td>Sigma-Aldrich</td>
			<td>A1343</td>
			<td></td>
		</tr>
		<tr>
			<td>Solvent Still</td>
			<td>Mbraun</td>
			<td>MB-SPS-800</td>
			<td></td>
		</tr>
		<tr>
			<td>Infared spectrometer</td>
			<td>Thermo</td>
			<td>Thermo Electron IR100</td>
			<td></td>
		</tr>
		<tr>
			<td>Nuclear Magnetic Resonance</td>
			<td>Bruker</td>
			<td></td>
			<td>400, 600 MHz</td>
		</tr>
		<tr>
			<td>LC/MS</td>
			<td>Thermo/Dionex</td>
			<td></td>
			<td>Single quad, ESI</td>
		</tr>
		<tr>
			<td>HRMS</td>
			<td>Agilent</td>
			<td>Synapt G2 S HDMS</td>
			<td></td>
		</tr>
		<tr>
			<td>Microwave reactor</td>
			<td>Anton Parr</td>
			<td>Anton Parr G10 Monowave 200</td>
			<td></td>
		</tr>
		<tr>
			<td>DBU</td>
			<td>Sigma-Aldrich</td>
			<td>139009</td>
			<td></td>
		</tr>
		<tr>
			<td>CCl3CN</td>
			<td>Sigma-Aldrich</td>
			<td>T53805</td>
			<td></td>
		</tr>
		<tr>
			<td>Pyridine</td>
			<td>Sigma-Aldrich</td>
			<td>270970</td>
			<td></td>
		</tr>
		<tr>
			<td>Acetone</td>
			<td>Fisher Scientific</td>
			<td>A18-20</td>
			<td>Tech. grade</td>
		</tr>
		<tr>
			<td>Phase separator</td>
			<td>Biotage</td>
			<td>120-1901-A</td>
			<td></td>
		</tr>
		<tr>
			<td>Rotary evaporator</td>
			<td>Buchi</td>
			<td>R-100</td>
			<td></td>
		</tr>
	</tbody>
</table>

one-pot microwave-assisted conversion of anomeric nitrate-esters to trichloroacetimidates

以下过程的目标是提供一个 2-叠-1-硝酸酯的一锅转换的示范对 trichloroacetimidate 糖捐赠者。经叠硝化后的 glycal, 产品 2-叠-1-硝酸酯可以在微波辅助照射下水解。这种转变通常是通过强亲核试剂和延长反应时间来实现的。微波辐照诱导水解, 在没有试剂的情况下, 反应时间短。在脱硝后, 中间 anomeric 醇在同一锅中转化为相应的 2-叠-1-trichloroacetimidate。

本文所述的技术在三 2-叠-1-硝酸酯的水池中被证明。在每种情况下, 反应的第一步是在20分钟内完成。
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/56610/56610fig2v3.jpg"> 图 2.有代表性的例子水解 (1 ->2), 和一锅转换 2-叠-1-硝酸酯的1 (1>3)。<a href="//cloudflare...

Watch this Scientific Journal Video about One-pot Microwave-assisted Conversion of Anomeric Nitrate-esters to Trichloroacetimidates at JoVE.com

One-pot Microwave-assisted Conversion of Anomeric Nitrate-esters to Trichloroacetimidates

硝酸酯 Anomeric Trichloroacetimidates 的单锅微波辅助转化

一个 2-叠-1-硝酸酯可以转换为相应的 2-叠-1-trichloroacetimidate 在一个锅的程序。该手稿的目的是演示微波反应器在碳水化合物合成中的效用。

The goal of the following procedure is to provide a demonstration of the one-pot conversion of a 2-azido-1-nitrate-ester to a trichloroacetimidate ...

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