Name: facile preparation of (2z,4e)-dienamides by the olefination of electron-deficient alkenes with allyl acetate
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注意：使用前请咨询所有相关材料安全数据表（MSDS）。所有交叉偶联反应应在密封氩气氛（1大气压）下在小瓶中进行。 丙烯酰胺与乙酸烯丙酯的合成制备丁二烯<ol><li>在120℃的烘箱中用兼容的磁力搅拌棒将螺旋盖小瓶（8mL）干燥2小时以上。使用前，将惰性气体吹入冷热瓶至室温。 </li><li>使用分析天平，称量3.7mg（〜3mol％，〜0.005mmol）[Ru（ p-色胺）Cl 2 ] 2...

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Stereochemistry, mechanism, and selected synthetic aspects.</a> Chem Rev. 89 (4), 863-927 (1989).</li><li>Stille, J. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Palladium-Catalyzed+Cross-Coupling+Reactions+of+Organotin+Reagents+with+Organic+Electrophiles.">The Palladium-Catalyzed Cross-Coupling Reactions of Organotin Reagents with Organic Electrophiles.</a> Angew Chem Int Ed. 25 (6), 508-524 (1986).</li><li>Zhang, Y., Cui, Z., Li, Z., Liu, Z. 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P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Selective+Alkenylation+and+Hydroalkenylation+of+Enol+Phosphates+through+Direct+C-H+Functionalization.">Selective Alkenylation and Hydroalkenylation of Enol Phosphates through Direct C-H Functionalization.</a> Angew Chem Int Ed. 54 (51), 15535-15539 (2015).</li><li>Kong, L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cobalt+(III)-Catalyzed+C-C+Coupling+of+Arenes+with+7-Oxabenzonorbornadiene+and+2-Vinyloxirane+via+C-H+Activation.">Cobalt (III)-Catalyzed C-C Coupling of Arenes with 7-Oxabenzonorbornadiene and 2-Vinyloxirane via C-H Activation.</a> Org Lett. 18 (15), 3802-3805 (2016).</li><li>Feng, C., Feng, D., Loh, T. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rhodium+(III)-catalyzed+C-H+allylation+of+electron-deficient+alkenes+with+allyl+acetates.">Rhodium (III)-catalyzed C-H allylation of electron-deficient alkenes with allyl acetates.</a> Chem Commun. 51 (2), 342-345 (2015).</li><li>Suzuki, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Dehydrative+Direct+C-H+Allylation+with+Allylic+Alcohols+under+[Cp*CoIII]+Catalysis.">Dehydrative Direct C-H Allylation with Allylic Alcohols under [Cp*CoIII] Catalysis.</a> Angew Chem Int Ed. 54 (34), 9944-9947 (2015).</li><li>Schwarz, K. J., Amos, J. L., Klein, J. C., Do, D. T., Snaddon, T. N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Uniting+C1-Ammonium+Enolates+and+Transition+Metal+Electrophiles+via+Cooperative+Catalysis:+The+Direct+Asymmetric+&#945;-Allylation+of+Aryl+Acetic+Acid+Esters.">Uniting C1-Ammonium Enolates and Transition Metal Electrophiles via Cooperative Catalysis: The Direct Asymmetric &#945;-Allylation of Aryl Acetic Acid Esters.</a> J Am Chem Soc. 138 (16), 5214-5217 (2016).</li><li>Zell, D., Bu, Q., Feldt, M., Ackermann, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mild+C-H/C-C+Activation+by+Z-Selective+Cobalt+Catalysis.">Mild C-H/C-C Activation by Z-Selective Cobalt Catalysis.</a> Angew Chem Int Ed. 55 (26), 7408-7412 (2016).</li><li>Li, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=N-Acyl+Amino+Acid+Ligands+for+Ruthenium(II)-Catalyzed+meta-C-H+tert-Alkylation+with+Removable+Auxiliaries.">N-Acyl Amino Acid Ligands for Ruthenium(II)-Catalyzed meta-C-H tert-Alkylation with Removable Auxiliaries.</a> J Am Chem Soc. 137 (43), 13894-13901 (2015).</li><li>Li, F., Yu, C., Zhang, J., Zhong, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Olefination+of+Electron-Deficient+Alkenes+with+Allyl+Acetate:+Stereo-+and+Regioselective+Access+to+(2Z,4E)-Dienamides.">Olefination of Electron-Deficient Alkenes with Allyl Acetate: Stereo- and Regioselective Access to (2Z,4E)-Dienamides.</a> Org Lett. 18 (18), 4582-4585 (2016).</li><li>Lehman, J. 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[Ru（ p-异氰酸酯）Cl 2 ] 2是一种便宜，易于使用的空气稳定且高活性的Ru基催化剂，具有优异的官能团耐受性，可在温和的反应条件下有效运行，得到CH / CH偶联丁二烯产物。使用银盐AgSbF 6作为可以抽出[Ru（ p-色胺）Cl 2 ] 2的氯化物以产生用于以下CH键活化的阳离子钌络合物的添加剂。然而，只有α取代和α，β-二取代的丙烯酰胺适...

Butadienes广泛存在，常见于许多天然产物，药物和生物活性分子1 。化学家已经作出了巨大的努力，开发出一种有效的，有选择性的，实用的合成1,3-二丁二烯合成方法2,3 。最近，开发了通过双乙烯基CH键活化的两种烯烃之间的直接交联，代表了具有高原子和逐步经济性的丁二烯的合成的有效策略。其中，钯催化的两种烯烃的交叉偶联引起了很大的关注， 通过烯基 - Pd物种4,5提供（ E，E ） - 配位丁二烯。例如，Liu的研究小组通过烯烃和乙酸烯丙酯的直接交叉偶联来开发Pd催化的丁二烯合成（ 图1 </strong&gt;和等式3 ） 4 。同时，由于烯烃CH环金属化事件，烯烃之间的官能团导向交叉偶联提供了具有优异（ Z，E ） - 立体选择性的丁二烯，代表了互补方法6 。迄今为止，一些指导小组，如烯醇化酶，酰胺，酯和磷酸酯已被成功地引入烯烃之间的交叉耦合，提供了一系列有价值和功能化的1,3-丁二烯。然而，有针对性的交叉偶联反应尚未得到发展，因为在实际应用中仍然有限的导向基团。特别地，通常需要化学计量的氧化剂以维持催化循环，这产生大量的有机和无机废物。使用富电子烯烃作为偶合配体的实例非常有限。 醋酸烯丙酯及其衍生物已经深入我在有机转化中被研究为强力的烯丙基化和烯化试剂，包括催化交叉偶联，富含电子的芳烃的Friedel-Crafts烯丙基化和电子缺乏的芳烃的催化CH活化（ 图1和方程1 ） 7 。最近，Loh集团开发了电子缺乏烯烃与乙酸烯丙酯的铑（III）催化CH烯丙基化，形成1,4-二烯（ 图1和方程2 ） 8 。同时，Kanai组通过使用Co（III）催化剂9报道了与烯丙醇的脱水直接CH烯丙基化。有趣的是，Snaddon及其同事们公开了一种新型的基于非催化剂的非对称α-烯丙基酯10的合作催化方法。最近，Ackermann集团报道了几个新的相关例子g便宜的Fe，Co和Mn催化剂11 。这些报告在烯丙基化和烯化反应中取得突破，但双键迁移和区域选择性差，通常是不可避免的，不易控制。因此，开发更有效和选择性的乙酸烯丙酯的反应模式来构建有价值的分子仍然是非常需要的。由于我们对通过 CH烯化的新型1,3-丁二烯合成的兴趣，我们假设可以将乙酸烯丙酯引入到电子缺陷烯烃的定向烯丙基化中，首先递送1,4-二烯。然后，在CC双键7的迁移异构化之后可以形成更多的热力学稳定的1,3-丁二烯，形成不能通过使用富电子的烯烃例如丙烯的交联而获得的二烯产物作为偶联配体6 。在这里，我们报告了廉价的Ru（III）催化的烯烃CH键烯烃n的丙烯酰胺与烯丙基乙酸酯在没有任何氧化剂的情况下，这为开创（ Z，E ） - 丁二烯（ 图1和方程4 ） 13创造了新的合成途径。

<table border="0" cellpadding="0" cellspacing="0" width="887">
	<tbody>
		<tr height="19">
			<td height="19" style="height:19px;width:284px;">Allyl Acetate</td>
			<td style="width:100px;">TCI</td>
			<td style="width:148px;">A0020</td>
			<td style="width:355px;">&#62; 98.0%(GC), 25 mL package</td>
		</tr>
		<tr height="38">
			<td height="38" style="height:38px;width:284px;">Dichloro(p-cymene)ruthenium(II) dimer</td>
			<td style="width:100px;">TCI</td>
			<td style="width:148px;">D2751</td>
			<td>&#62; 95.0%(T), 5 g package</td>
		</tr>
		<tr height="19">
			<td height="19" style="height:19px;">Silver hexafluoroantimonate</td>
			<td style="width:100px;">TCI</td>
			<td style="width:148px;">S0463</td>
			<td>&#62; 97.0%(T),&#160; 5 g package</td>
		</tr>
		<tr height="19">
			<td height="19" style="height:19px;">1,2-Dichloroethane</td>
			<td style="width:100px;">TCI</td>
			<td style="width:148px;">D0364</td>
			<td>&#62; 99.5%(GC), 500 g package</td>
		</tr>
		<tr height="19">
			<td height="19" style="height:19px;">Rotavapor</td>
			<td style="width:100px;">EYELA</td>
			<td style="width:148px;">N-1200A</td>
			<td>Use to dry solvent</td>
		</tr>
		<tr height="19">
			<td height="19" style="height:19px;width:284px;">Silica gel</td>
			<td style="width:100px;">Merck</td>
			<td style="width:148px;">107734</td>
			<td>Silica gel 60 (0.063-0.2 mm), for column chromatoraphy</td>
		</tr>
	</tbody>
</table>

facile preparation of (2z,4e)-dienamides by the olefination of electron-deficient alkenes with allyl acetate

通过乙烯基CH键活化，两种烯烃之间的直接交叉耦合代表了合成具有高原子和经济经济性的丁二烯的有效策略。然而，这种功能导向的交叉偶联反应还没有被开发出来，因为在实际应用中仍然有限的导向基团。特别地，通常需要化学计量的氧化剂，产生大量的废物。由于我们对新型1,3-丁二烯合成的兴趣，我们描述了使用乙酸烯丙酯和没有外部氧化剂的电子缺陷烯烃的钌催化烯化反应。选择2-苯基丙烯酰胺和乙酸烯丙酯的反应作为模型反应，在最佳条件下，以80％的分离收率获得所需的二烯产物，具有良好的立体选择性（ Z，E / Z，Z = 88:12）：[ Ru（ p-色胺）Cl 2 ] 2 （3mol％）和AgSbF 6 （20mol％）在DCE中在110℃或16小时。通过优化的催化条件，研究了代表性的α - 和/或β-取代的丙烯酰胺，并且所有反应都是平滑的，而不管脂族或芳族基团。此外，不同的N-取代的丙烯酰胺已被证明是良好的底物。此外，我们检查了不同烯丙基衍生物的反应性，表明醋酸氧化物对金属的螯合对催化过程至关重要。还进行氘标记实验以研究反应机理。仅观察到丙烯酰胺上的Z选择性H / D交换，表明可逆的环金属化事件。此外，在分子间同位素研究中观察到3.2的动力学同位素效应（KIE），表明烯烃CH金属化步骤可能参与速率确定步骤。

我们的努力集中在从丙烯酰胺和乙酸烯丙酯制备1,3-丁二烯。 表1说明了使用[Ru（β-异氰酸酯）Cl 2 ] 2作为催化剂的条件优化，包括各种添加剂和溶剂的筛选。在筛选出一系列有代表性的溶剂后，我们很高兴地发现，产物产率显着提高到80％，选择性好（ Z，E / Z，Z = 88:12）。通过NOESY NMR...

Watch this Scientific Journal Video about Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate at JoVE.com

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

这里描述了电子缺乏烯烃与乙酸烯丙酯的钌催化烯化反应。通过使用氨基羰基作为引导基团，该外部无氧化剂方案具有高效率和良好的立体选择性和开放的新的合成途径（ Z ， E ） - 丁二烯骨架。

（2<em&gt;ž</em&gt;，4<em&gt;电子</em&gt;） - 通过电子缺陷烯烃与烯丙基乙酸酯的烯化反应制备二烯酰胺

Direct cross-coupling between two alkenes via vinylic C-H bond activation represents an efficient strategy for the synthesis of butadienes with high ...

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Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Dienes, Conjugated Pi Systems, and Pericyclic Reactions

Alkene Structure and Reactivity

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