这项工作得到了中国国家自然科学基金 (21471037)、广东省杰出青年学者基金 (15ZK0307)、广东科技规划项目 (2017A050506051) 和香港特区研究资助委员会 [GRF 11303414]。

警告: 使用前请查阅所有相关的材料安全数据表。二硫化甲和 thiomethoxide 钠是强烈的恶臭, 应在通风罩中处理。金属钠具有极强的反应性, 对潜在的火灾和爆炸危险需要特别的安全措施。除使用油烟机外, 个人防护设备 (安全眼镜、手套、实验室大衣、全长长裤和闭趾鞋) 应适当采用。以下程序的一部分涉及标准的无空气处理技术。
1. Thiomethoxide 钠的制备 (CH3SNa)
<ol><li>将200毫升 Schlenk 烧瓶连接到真空气体歧管。疏散烧瓶, 然后用 N2三次回填它, 这样瓶子里就充满了一个稍正的 N2压力。 注意: 文献中简要提到了一种类似的编写 CH3SNa 的方法, 但没有提供详细的程序27,28。</li>
	<li>从煤油油藏取出一大块金属钠。用纸巾擦拭表面的残余油, 用刀子刮掉表面上的氧化物层。快速切割6.7 克的金属钠 (0.29 摩尔) 成小块 (e. g, 约大豆大小), 并立即将小块转移到200毫升 Schlenk 瓶下的计数器流 N2。立即用隔膜封住烧瓶。 注: 为了减少对空气的接触, 你可以从6.7 克的数量中切出钠, 并根据实际使用的钠量调整 THF 和二甲硫的含量。</li>
	<li>将80毫升无水、无气的 THF 从 Schlenk 线置于 N2保护下的烧瓶中通过套管。提取14.0 毫升二甲硫 (0.158 摩尔; 用 n2预先清除) 放入注射器中, 并将其注入到在 N2保护下的烧瓶中滴下。 注意: 二甲基二硫恶臭, 应在通风罩中处理。</li>
	<li>用地面玻璃塞子代替隔膜。将反应混合物在室温下搅拌24小时, 然后在60摄氏度处搅动3小时。 注: 反应混合物在室温下搅拌时粘性变稠;当加热到60摄氏度时, 混合物可以更容易搅拌, 从而加快反应完成。</li>
	<li>当温度保持在60摄氏度左右时, 使用 N2 (0.2 升/分钟) 的流来吹散 THF 溶剂和过量二甲基二硫醚, 直到出现干固体。使用冷阱 (e. g, 丙酮/干冰) 收集流出的 THF 和二甲硫。</li>
	<li>将剩余的固体混合物与油泵一起疏散约2小时, 除去残留的 THF 和二甲硫, 然后用 N2将其回填, 以获得淡黄色固体 (19.8 克, 97%)。将固态产品 CH3SNa 存储在黑暗中的氮气气氛中。 注: 为了保护真空泵, 在泵浦过程中应使用冷阱。</li>
</ol>2. 制备23、67、1011-hexakis (pentanoylthio) 苯并菲 (HVaTT) 作为受保护的硫醇链接器
<ol><li>将 0.664 g 的 CH3SNa (9.0 毫摩尔) 加载到50毫升 Schlenk 烧瓶中, 在 n 2 ( i.e) 的计数器流下, 在 n 2 保护下连接到真空气体歧管. 注意: CH3SNa 对空气敏感, 容易吸收水分。为了尽量减少对空气的接触, 你可以快速地称量出特定的量并将其添加到烧瓶中, 然后调整其他反应物的数量, 23, 67, 1011-hexabromotriphenylene (HBT), 相应地。 警告: 实心 CH3SNa 具有强烈的气味, 应在通风罩中处理。</li>
	<li>在 N2的计数器流下, 向烧瓶中添加0.216 克 HBT (0.30 毫摩尔), 并用隔膜封住烧瓶。</li>
	<li>将10毫升无水和无气 13-二甲基 2 imidazolidinone (DMEU) 从 Schlenk 线的 N2保护下通过套管转移到烧瓶中。</li>
	<li>用普通的玻璃塞子代替隔膜, 搅拌反应混合物, 用盐浴将其加热到240摄氏度, 在 N2下加48小时。</li>
	<li>对反应进展的薄层监测: 在 N2下, 使用玻璃吸管提取反应混合物的小整除 (约0.1 毫升), 并立即将其注入 valeroyl 氯化物 (约0.1 毫升) 在塑料中的整齐液体样品中。离心瓶, 然后摇1分钟;混合物应立即变成混浊与灰白色的颜色。加入0.4 毫升去离子水和0.1 毫升醋酸乙酯, 关闭瓶盖, 摇晃几秒钟。 注: 如果反应已经完成, 就不会出现在水层和乙酸乙酯之间的任何东西。如果不是, 将出现两层之间的白色不溶物。</li>
	<li>吸管上半部分, 并用它来发现薄层色板。用1:4 乙酸乙酯/石油醚开发薄层色谱板。对于一个完整的反应, 目标分子显示为一个规则点围绕 Rf = 0.4 在紫外线灯下。</li>
	<li>关掉暖气, 把反应瓶从盐浴中冷却到室温, 然后用冰浴把瓶子冷却到摄氏0摄氏度。</li>
	<li>用注射器在 N2下注入1.5 毫升的 valeroyl 氯 (12.6 毫摩尔) 到烧瓶中 (在大约2分钟的时间内)。保持搅拌在0°c 为2小时注: 在低温下添加 valeroyl 氯化物, 有助于减少副产品的生成。</li>
	<li>将混合物倒入50毫升的冰水中, 用醋酸乙酯 (3 30 毫升) 提取。然后用水 (6 60 毫升) 清洗复合有机层, 干燥过无水 MgSO4, 并通过旋转蒸发器去除挥发物。</li>
	<li>以1:10 乙酸乙酯/石油醚为淋洗, 用柱层析分离油性原油产品, 在溶剂的回转蒸发后提供淡黄色油性产物。用1:4 乙酸乙酯/石油醚开发薄层色谱板, Rf = 0.4。使用下面的研磨步骤进一步净化油性产品。</li>
	<li>添加5毫升的 methanolto 的油性产品, 油脂实验2分钟收集的结果白色固体使用吸滤 (产量: 59%)。</li>
</ol>3. HTT-铅骨架材料单晶的制备
<ol><li>混合11.4 毫克的 PbOAc·3H2O (0.030 毫摩尔) 在1.0 毫升乙烯二胺在一瓶, 以作出明确的解决办法。</li>
	<li>负载9.1 毫克的 HVaTT (0.010 毫摩尔), 2.0 毫升的脱气甲醇溶液的氢氧化钠 (70 毫摩尔/升), 和1.0 毫升乙烯二胺成空10毫升瓶和油脂实验5分钟。</li>
	<li>将 PbOAc 溶液添加到微气泡 HVaTT 混合物中。然后用 N2将反应混合物泡在1分钟内, 然后戴上螺钉盖密封瓶子。</li>
	<li>加热瓶在90°c 在一个烤箱48小时, 其次是自然冷却到室温, 在此期间形成了黄橙, 八面体单晶, 适合单晶 x 射线衍射研究 (产量: 45%)。</li>
	<li>吸入过滤掉晶体并迅速用甲醇清洗。用玻璃吸管将晶体转移到含有无气甲醇 (5 毫升) 的瓶子中, 以存放在室温下。</li>
</ol>4. 百草枯二碘化与 HTT 铅晶体的相互作用
<ol><li>使用玻璃巴斯德吸管从甲醇的股票中提取出几粒 HTT Pb 单晶, 并将其放到培养皿上 (直径35毫米和深度10毫米)。用纸巾或滤纸 (或让甲醇自然干燥) 吸收甲醇液体, 然后落到晶体上几滴水溶液的百草枯二碘化 (0.1%, w/w)。</li>
	<li>用眼睛或显微镜观察晶体的颜色变化。</li>
</ol>

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W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Early+metal+thiolato+species+as+metalloligands+in+the+formation+of+early/late+heterobimetallic+complexes:+syntheses+and+molecular+structures+of+Cp2Ti(SMe)2,+Cp2V(SMe)2,+(Cp2Ti(&#181;-SMe)2)2Ni+and+(Ni(&#181;-SMe)2)6.">Early metal thiolato species as metalloligands in the formation of early/late heterobimetallic complexes: syntheses and molecular structures of Cp2Ti(SMe)2, Cp2V(SMe)2, (Cp2Ti(&#181;-SMe)2)2Ni and (Ni(&#181;-SMe)2)6.</a> Organometallics. 8 (12), 2836-2843 (1989).</li><li>Chakraborty, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Sodium+methanethiolate.">Sodium methanethiolate.</a> e-EROS Encycl Reagents Org Synth. , 1-5 (2014).</li><li>Huang, 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=A+semiconducting+gyroidal+metal-sulfur+framework+for+chemiresistive+sensing.">A semiconducting gyroidal metal-sulfur framework for chemiresistive sensing.</a> J Mater Chem A. 5 (31), 16139-16143 (2017).</li><li>He, 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=Building+thiol+and+metal-thiolate+functions+into+coordination+nets:+Clues+from+a+simple+molecule.">Building thiol and metal-thiolate functions into coordination nets: Clues from a simple molecule.</a> J Solid State Chem. 182 (7), 1821-1826 (2009).</li><li>Yee, K. -. K., 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=Effective+Mercury+Sorption+by+Thiol-Laced+Metal-Organic+Frameworks:+in+Strong+Acid+and+the+Vapor+Phase.">Effective Mercury Sorption by Thiol-Laced Metal-Organic Frameworks: in Strong Acid and the Vapor Phase.</a> J Am Chem Soc. 135 (21), 7795-7798 (2013).</li><li>Yee, K. -. K., 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=Room-temperature+acetylene+hydration+by+a+Hg(II)-laced+metal-organic+framework.">Room-temperature acetylene hydration by a Hg(II)-laced metal-organic framework.</a> Chem Commun. 51 (54), 10941-10944 (2015).</li><li>Gui, B., 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=Tackling+poison+and+leach:+catalysis+by+dangling+thiol-palladium+functions+within+a+porous+metal-organic+solid.">Tackling poison and leach: catalysis by dangling thiol-palladium functions within a porous metal-organic solid.</a> Chem Commun. 51 (32), 6917-6920 (2015).</li><li>He, J., Zeller, M., Hunter, A. D., Xu, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Functional+shakeup+of+metal-organic+frameworks:+the+rise+of+the+sidekick.">Functional shakeup of metal-organic frameworks: the rise of the sidekick.</a> CrystEngComm. 17 (48), 9254-9263 (2015).</li></ol>

作者没有什么可透露的。

溴组与 thiomethoxide 阴离子的反应显然首先产生了甲基硫醚类, 然后 demethylated 过量 thiomethoxide 提供 thiolate 负离子产品。为了确保完全转化为所需的 thiolate 阴离子 (特别是 polybromide 基板如 HBT), 长时间加热的旺盛条件 (例如, 240 °c 超过48小时) 与大量过量钠 thiomethoxide (例如, 超过三倍的摩尔的溴组) 是必不可少的。防止反应物和产物的 thiolate 种类的氧化也需要氮气保护。酰化步骤 (例?...

目前有极大的兴趣使用强, 极化金属硫 (e. g., 金属 thiolate) 链接, 用于构造具有增强电催化和导电性能的开放框架材料1,2,3,4,5,6,7,8,9,10. 除了在延长的状态下促进电子相互作用和运输外, 软和共价键金属硫的连接也给水环境中的应用提供了更好的稳定性。在含硫的积木中, 对称的, 多齿多环芳烃积木, 如 23, 67, 1011-苯并菲 hexathiol (HTT)9,11,12, 13,14不仅提供高度极化的π电子, 而且在框架设计和合成方面也提供了明显的优势。首先, 刚性和对称的苯并菲核心, 结合螯合 dithiolene 组的 HTT, 有助于锁定金属离子在常规的粘合图案, 简化预期网络的结构预测7,15. 与硫磺连接器的刚性和开放几何结合, 具有大量孔隙特征的框架结构通常可以在固态中实现。
在组装硫醇设备金属 orangic 框架 (MOF) 材料的一个主要挑战是植根于有机链接分子的合成。在经典的协议中, 硫醇基团必须是从苯酚组中提取的, 使用纽曼-Kwart 重排O-芳 thiocarbamate 前体16,17,18。然而, 这种方法涉及对苯酚前体分子的精心制备步骤以及高温固相转化的潜在并发症。另一种制造硫醇的方法是在苛刻的条件下使用 thioethers 的还原脱, 例如, 液态氨水中的钠金属 19, 20, 21, 22, 而不是与羧基和其他许多捐助函数兼容, 用于网络建设。
相比之下, 此处提出的协议具有多种优点: 安全性、方便性、成本效益以及与其他功能组 (e. g、carbonitrile 和吡啶) 的兼容性。通过大力加热一般廉价的芳香卤化物 (e. g, hexabromotriphenylene) 和 thiomethoxide 阴离子, thiolate 负离子产生 (通过甲基硫醚类中间产物), 然后酰给稳定和易于处理的硫酯产品-所有在一个锅。
我们还将描述一个程序, 利用硫酯分子作为连接器的蒙面形式, 以获取单一晶体半导体和多孔金属 dithiolene 网络。不同于高度反应自由站立的硫醇, 它倾向于分解和复杂化金属 thiolate 开放框架的结晶, 硫酯可以容易地被切开(e. g, 由氢氧化钠或乙二胺)就地提供硫醇类, 有助于减轻硫醇单位和金属中心之间的反应, 从而改善结晶。
这种制备硫醇/硫酯的议定书尚未被其他群体广泛用于金属-硫框架的新兴领域, 尽管 thiolate 阴离子的烷基芳 thioethers 的亲核 dealkylations 已经被有机化学家23,24,25,26。通过展示这种有效的 thioesters 合成方法及其用于促进金属硫网络的结晶, 我们希望进一步努力弥合合成有机化学与固态化学, 有助于快速、健康地发展多孔骨架。

<table border="0" cellpadding="0" cellspacing="0" width="850">
	<tbody>
		<tr height="22">
			<td height="22" style="height:22px;width:216px;">Bromine</td>
			<td style="width:348px;">DAMAO CHEMICAL REAGENT FACTORY</td>
			<td style="width:119px;">7726-95-6</td>
			<td style="width:167px;">Highly toxic</td>
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		<tr height="21">
			<td height="21" style="height:21px;">Triphenylene&#160;&#160;</td>
			<td style="width:348px;">HWRK Chem</td>
			<td style="width:119px;">HWG45510</td>
			<td></td>
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			<td height="21" style="height:21px;">Iron powder</td>
			<td style="width:348px;">Sigma-Aldrich</td>
			<td style="width:119px;">12310</td>
			<td></td>
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		<tr height="24">
			<td height="24" style="height:24px;width:216px;">Nitrobenzene</td>
			<td style="width:348px;">DAMAO CHEMICAL REAGENT FACTORY</td>
			<td style="width:119px;">2934</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;width:216px;">Diethyl ether&#160;</td>
			<td style="width:348px;">DAMAO CHEMICAL REAGENT FACTORY</td>
			<td style="width:119px;">48</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;width:216px;">Dichloromethane</td>
			<td style="width:348px;">DAMAO CHEMICAL REAGENT FACTORY</td>
			<td>3067</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Sodium metal</td>
			<td style="width:348px;">J&#38;K</td>
			<td style="width:119px;">WM-NMS-54-25X-50G</td>
			<td>Air sensitive</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Tetrahydrofuran</td>
			<td style="width:348px;">J&#38;K</td>
			<td style="width:119px;">315353</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Dimethyl disulfide</td>
			<td style="width:348px;">INTERNATIONAL LABORATORY USA</td>
			<td style="width:119px;">726415</td>
			<td></td>
		</tr>
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			<td height="21" style="height:21px;">1,3-Dimethyl-2-imadazolidinone</td>
			<td style="width:348px;">J&#38;K</td>
			<td style="width:119px;">50483</td>
			<td>Dried over 4&#197; sieves</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Valeryl&#160; chloride</td>
			<td style="width:348px;">J&#38;K</td>
			<td style="width:119px;">99590</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Methanol</td>
			<td style="width:348px;">Guangzhou Chemical Reagent Factory</td>
			<td>2334</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Sodium hydroxide</td>
			<td style="width:348px;">Guangzhou Chemical Reagent Factory</td>
			<td style="width:119px;">1588</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Ethylene diamine</td>
			<td style="width:348px;">Riedel-de Ha&#235;n</td>
			<td style="width:119px;">15070</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Lead acetate trihydrate</td>
			<td>PEKING CHEMICAL WORKE</td>
			<td style="width:119px;">861218</td>
			<td></td>
		</tr>
	</tbody>
</table>

synthesis of a thiol building block for the crystallization of a semiconducting gyroidal metal-sulfur framework

我们提出了一种制备硫酯分子的方法, 作为硫醇连接器的掩蔽形式及其在高度有序的单晶态中获取半导体和多孔金属 dithiolene 网络的利用。不同于高度反应自由站立的硫醇, 它倾向于分解和复杂化金属 thiolate 开放框架的结晶, 硫酯反应原位提供硫醇种类, 为缓和之间的反应硫醇单位和金属中心, 从而改善结晶。具体地说, 硫酯是在一锅工序中合成的: 芳香溴 (hexabromotriphenylene) 在剧烈的条件下与过量 thiomethoxide 反应, 首先形成硫醚类中间产物。硫醚类然后 demethylated 过剩的 thiomethoxide 提供 thiolate 负离子, 酰形成硫酯产品。用标准柱层析法对硫酯进行了简便纯化, 然后直接在骨架合成中使用, 其中氢氧化钠和乙二胺用于恢复原位硫酯到硫醇连接器组装单晶 Pb (II)-dithiolene 网络。与其他的硫醇合成方法 (e. g) 相比, 用钠金属和液态氨裂解烷基硫醚类, 这里的硫酯合成使用简单的条件和经济试剂。此外, 硫酯产品稳定, 可以方便地处理和储存。更重要的是, 与访问水晶金属 thiolate 开放框架的一般困难相反, 我们证明使用硫酯进行原位的硫醇连接器的形成大大提高了固态的结晶度. 产品。我们打算通过披露硫酯的合成协议以及水晶骨架固体, 鼓励在技术上重要的金属硫框架方面开展更广泛的研究工作。

HVaTT 分子的红外光谱 (由 KBr 颗粒法收集) 以其最大吸收率为1700厘米-1, 按照硫酯官能团的羰基拉伸。1HVaTT (400 MHz、CDCl3) 的 H 核磁共振谱显示了δ8.47 中的一个单线, 从芳香氢, 连同 4 multiplets 从脂肪族质子: δ 8.47 (s, 6H, CHAr), 2.75-2.72 (t, J = 7.4, 12H, CH2), 1.81-1. 77 (m,12H, ch2), 1.50-1. 45 (dd, J = 7.4, 12H, CH2), 1.00-0. 97 (t, J</em...

Watch this Scientific Journal Video about Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework at JoVE.com

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

在这里, 我们提出了一锅, 过渡无金属合成的硫醇和 thioesters 从芳香卤化物和 thiomethoxide 钠, 其次是制备的单一晶体的金属 dithiolene 网络使用硫醇物种产生的就地从更稳定和易于驾驭的硫酯。

半导体回转金属硫框架结晶的硫醇构建块的合成

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and ...

synthesis-thiol-building-block-for-crystallization-semiconducting

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Organic Chemistry

Chemistry

Unit 1

Ethers, Epoxides, Sulfides

SCIENTISTS IN ACTION

8.9K 次观看.  Guangdong University of Technology. 在这里, 我们提出了一锅, 过渡无金属合成的硫醇和 thioesters 从芳香卤化物和 thiomethoxide 钠, 其次是制备的单一晶体的金属 dithiolene 网络使用硫醇物种产生的就地从更稳定和易于驾驭的硫酯。

视频: Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

Preparation and Use of Samarium Diiodide (SmI2) in Organic Synthesis: The Mechanistic Role of HMPA and Ni(II) Salts in the Samarium Barbier Reaction

Although initially considered an esoteric reagent, SmI2 has become a common tool for synthetic organic chemists. SmI2 is generated through the addition of molecular iodine to samarium metal in THF.1,2-3 It is a mild and selective single electron reductant and its versatility is a result of its ability to initiate a wide range of reductions including C-C bond-forming and cascade or sequential reactions. SmI2 can reduce a variety of functional groups including sulfoxides and sulfones, phosphine oxides, epoxides, alkyl and aryl halides, carbonyls, and conjugated double bonds.2-12 One of the fascinating features of SmI-2-mediated reactions is the ability to manipulate the outcome of reactions through the selective use of cosolvents or additives. In most instances, additives are essential in controlling the rate of reduction and the chemo- or stereoselectivity of reactions.13-14 Additives commonly utilized to fine tune the reactivity of SmI2 can be classified into three major groups: (1) Lewis bases (HMPA, other electron-donor ligands, chelating ethers, etc.), (2) proton sources (alcohols, water etc.), and (3) inorganic additives (Ni(acac)2, FeCl3, etc).3
Understanding the mechanism of SmI2 reactions and the role of the additives enables utilization of the full potential of the reagent in organic synthesis. The Sm-Barbier reaction is chosen to illustrate the synthetic importance and mechanistic role of two common additives: HMPA and Ni(II) in this reaction. The Sm-Barbier reaction is similar to the traditional Grignard reaction with the only difference being that the alkyl halide, carbonyl, and Sm reductant are mixed simultaneously in one pot.1,15 Examples of Sm-mediated Barbier reactions with a range of coupling partners have been reported,1,3,7,10,12 and have been utilized in key steps of the synthesis of large natural products.16,17 Previous studies on the effect of additives on SmI2 reactions have shown that HMPA enhances the reduction potential of SmI2 by coordinating to the samarium metal center, producing a more powerful,13-14,18 sterically encumbered reductant19-21 and in some cases playing an integral role in post electron-transfer steps facilitating subsequent bond-forming events.22 In the Sm-Barbier reaction, HMPA has been shown to additionally activate the alkyl halide by forming a complex in a pre-equilibrium step.23
Ni(II) salts are a catalytic additive used frequently in Sm-mediated transformations.24-27 Though critical for success, the mechanistic role of Ni(II) was not known in these reactions. Recently it has been shown that SmI2 reduces Ni(II) to Ni(0), and the reaction is then carried out through organometallic Ni(0) chemistry.28
These mechanistic studies highlight that although the same Barbier product is obtained, the use of different additives in the SmI2 reaction drastically alters the mechanistic pathway of the reaction. The protocol for running these SmI2-initiated reactions is described.

Preparation and Use of Samarium Diiodide SmI2 in Organic Synthesis: The Mechanistic Role of HMPA and NiII Salts in the Samarium Barbier Reaction

A straightforward procedure for the preparation of samarium diiodide (SmI2) in THF is described. The role of two main additives namely hexamethylphosphoramide (HMPA) and Ni(acac)2 in Sm mediated reactions is demonstrated in the Sm-Barbier reaction.

二碘化钐的制备和使用（SMI<sub&gt; 2</sub&gt;）在有机合成中:HMPA和镍（II）盐的钐巴尔比耶反应的机理作用

Although initially considered an esoteric reagent, SmI2 has become a common tool for synthetic organic chemists. SmI2 is generated through the addition of ...

科研

化学

Synthesis and Purification of Iodoaziridines Involving Quantitative Selection of the Optimal Stationary Phase for Chromatography

The highly diastereoselective preparation of cis-N-Ts-iodoaziridines through reaction of diiodomethyllithium with N-Ts aldimines is described. Diiodomethyllithium is prepared by the deprotonation of diiodomethane with LiHMDS, in a THF/diethyl ether mixture, at -78 &#176;C in the dark. These conditions are essential for the stability of the LiCHI2 reagent generated. The subsequent dropwise addition of N-Ts aldimines to the preformed diiodomethyllithium solution affords an amino-diiodide intermediate, which is not isolated. Rapid warming of the reaction mixture to 0 &#176;C promotes cyclization to afford iodoaziridines with exclusive cis-diastereoselectivity. The addition and cyclization stages of the reaction are mediated in one reaction flask by careful temperature control.
Due to the sensitivity of the iodoaziridines to purification, assessment of suitable methods of purification is required. A protocol to assess the stability of sensitive compounds to stationary phases for column chromatography is described. This method is suitable to apply to new iodoaziridines, or other potentially sensitive novel compounds. Consequently this method may find application in range of synthetic projects. The procedure involves firstly the assessment of the reaction yield, prior to purification, by 1H NMR spectroscopy with comparison to an internal standard. Portions of impure product mixture are then exposed to slurries of various stationary phases appropriate for chromatography, in a solvent system suitable as the eluent in flash chromatography. After stirring for 30 min to mimic chromatography, followed by filtering, the samples are analyzed by 1H NMR spectroscopy. Calculated yields for each stationary phase are then compared to that initially obtained from the crude reaction mixture. The results obtained provide a quantitative assessment of the stability of the compound to the different stationary phases; hence the optimal can be selected. The choice of basic alumina, modified to activity IV, as a suitable stationary phase has allowed isolation of certain iodoaziridines in excellent yield and purity.

A protocol for the diastereoselective one-pot preparation of cis-N-Ts-iodoaziridines is described. The generation of diiodomethyllithium, addition to N-Ts aldimines and cyclization of the amino gem-diiodide intermediate to iodoaziridines is demonstrated. Also included is a protocol to rapidly and quantitatively assess the most appropriate stationary phase for purification by chromatography.

合成和Iodoaziridines纯化涉及定量选择最优固定相的色谱

The highly diastereoselective preparation of cis-N-Ts-iodoaziridines through reaction of diiodomethyllithium with N-Ts aldimines is described. ...

Synthesis and Exfoliation of Discotic Zirconium Phosphates to Obtain Colloidal Liquid Crystals

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and engineers. Growth of such anisotropic nanocrystals through a simple chemical method is a challenging task. In this study, we fabricate discotic nanodisks of zirconium phosphate [Zr(HPO4)2&#183;H2O] as a model material using hydrothermal, reflux and microwave-assisted methods. Growth of crystals is controlled by duration time, temperature, and concentration of reacting species. The novelty of the adopted methods is that discotic crystals of size ranging from hundred nanometers to few micrometers can be obtained while keeping the polydispersity well within control. The layered discotic crystals are converted to monolayers by exfoliation with tetra-(n)-butyl ammonium hydroxide [(C4H9)4NOH, TBAOH]. Exfoliated disks show isotropic and nematic liquid crystal phases. Size and polydispersity of disk suspensions is highly important in deciding their phase behavior.

A two dimensional model material of discotic zirconium phosphate was developed. The inorganic crystal with lamellar structure was synthesized by hydrothermal, reflux, and microwave-assisted methods. On exfoliation with organic molecules, layered crystals can be converted to monolayers, and nematic liquid crystal phase was formed at sufficient concentration of monolayers.

合成与盘状磷酸盐锆剥落获取胶体液晶

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and ...

Synthesis of Programmable Main-chain Liquid-crystalline Elastomers Using a Two-stage Thiol-acrylate Reaction

This study presents a novel two-stage thiol-acrylate Michael addition-photopolymerization (TAMAP) reaction to prepare main-chain liquid-crystalline elastomers (LCEs) with facile control over network structure and programming of an aligned monodomain. Tailored LCE networks were synthesized using routine mixing of commercially available starting materials and pouring monomer solutions into molds to cure. An initial polydomain LCE network is formed via a self-limiting thiol-acrylate Michael-addition reaction. Strain-to-failure and glass transition behavior were investigated as a function of crosslinking monomer, pentaerythritol tetrakis(3-mercaptopropionate) (PETMP). An example non-stoichiometric system of 15 mol% PETMP thiol groups and an excess of 15 mol% acrylate groups was used to demonstrate the robust nature of the material. The LCE formed an aligned and transparent monodomain when stretched, with a maximum failure strain over 600%. Stretched LCE samples were able to demonstrate both stress-driven thermal actuation when held under a constant bias stress or the shape-memory effect when stretched and unloaded. A permanently programmed monodomain was achieved via a second-stage photopolymerization reaction of the excess acrylate groups when the sample was in the stretched state. LCE samples were photo-cured and programmed at 100%, 200%, 300%, and 400% strain, with all samples demonstrating over 90% shape fixity when unloaded. The magnitude of total stress-free actuation increased from 35% to 115% with increased programming strain. Overall, the two-stage TAMAP methodology is presented as a powerful tool to prepare main-chain LCE systems and explore structure-property-performance relationships in these fascinating stimuli-sensitive materials.

A novel methodology is presented to synthesize and program main-chain liquid-crystalline elastomers using commercially available starting monomers. A wide range of thermomechanical properties was tailored by adjusting the amount of crosslinker, while the actuation performance was dependent on the amount of applied strain during programming.

的可编程主链液晶性弹性体用双级硫醇丙烯酸酯反应合成

This study presents a novel two-stage thiol-acrylate Michael addition-photopolymerization (TAMAP) reaction to prepare main-chain liquid-crystalline ...

Synthesis of Cd-free InP/ZnS Quantum Dots Suitable for Biomedical Applications

Fluorescent nanocrystals, specifically quantum dots, have been a useful tool for many biomedical applications. For successful use in biological systems, quantum dots should be highly fluorescent and small/monodisperse in size. While commonly used cadmium-based quantum dots possess these qualities, they are potentially toxic due to the possible release of Cd2+ ions through nanoparticle degradation. Indium-based quantum dots, specifically InP/ZnS, have recently been explored as a viable alternative to cadmium-based quantum dots due to their relatively similar fluorescence characteristics and size. The synthesis presented here uses standard hot-injection techniques for effective nanoparticle growth; however, nanoparticle properties such as size, emission wavelength, and emission intensity can drastically change due to small changes in the reaction conditions. Therefore, reaction conditions such temperature, reaction duration, and precursor concentration should be maintained precisely to yield reproducible products. Because quantum dots are not inherently soluble in aqueous solutions, they must also undergo surface modification to impart solubility in water. In this protocol, an amphiphilic polymer is used to interact with both hydrophobic ligands on the quantum dot surface and bulk solvent water molecules. Here, a detailed protocol is provided for the synthesis of highly fluorescent InP/ZnS quantum dots that are suitable for use in biomedical applications.

In this protocol, the synthesis of Cd-free InP/ZnS quantum dots (QDs) is detailed. InP-based QDs are gaining popularity due to the toxicity of Cd2+ ions that may be released through nanoparticle degradation. After synthesis, QDs are solubilized in water using an amphiphilic polymer for use in biomedical applications.

镉免费的InP /硫化锌量子点的合成适合生物医学应用

Fluorescent nanocrystals, specifically quantum dots, have been a useful tool for many biomedical applications. For successful use in biological systems, ...

HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately 200 different odorant compounds in addition to vanillin. The natural extraction of vanillin (from the orchid Vanilla planifolia, Vanilla tahitiensis and Vanilla pompon) represents only 1% of the worldwide production and since this process is expensive and very long, the rest of the production of vanillin is synthesized. Many biotechnological approaches can be used for the synthesis of vanillin from lignin, phenolic stilbenes, isoeugenol, eugenol, guaicol, etc., with the disadvantage of harming the environment since these processes use strong oxidizing agents and toxic solvents. Thus, eco-friendly alternatives on the production of vanillin are very desirable and thus, under current investigation. Porous coordination polymers (PCPs) are a new class of highly crystalline materials that recently have been used for catalysis. HKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzene-tricarboxylate) is a very well known PCP which has been extensively studied as a heterogeneous catalyst. Here, we report a synthetic strategy for the production of vanillin by the oxidation of trans-ferulic acid using HKUST-1 as a catalyst.

The conversion of trans-ferulic acid to vanillin was achieved by heterogeneous catalysis. HKUST-1 was employed in this synthesis and the essential step in the catalytic process was the generation of unsaturated metal sites. Thus, when the catalyst was activated under vacuum, full vanillin conversion (yield of 95%) was obtained.

科大-1作为香兰素的合成的非均相催化剂

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately ...

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the development of antibody drug conjugates (ADCs) and nanomedicine, fluorescent microscopy and systems chemistry. For many of these applications, specificity of the bioconjugation method used is of prime concern. The Michael addition of maleimides with cysteine(s) on the target proteins is highly selective and proceeds rapidly under mild conditions, making it one of the most popular methods for protein bioconjugation.
We demonstrate here the modification of the only surface-accessible cysteine residue on yeast cytochrome c with a ruthenium(II) bisterpyridine maleimide. The protein bioconjugation is verified by gel electrophoresis and purified by aqueous-based fast protein liquid chromatography in 27% yield of isolated protein material. Structural characterization with MALDI-TOF MS and UV-Vis is then used to verify that the bioconjugation is successful. The protocol shown here is easily applicable to other cysteine - maleimide coupling of proteins to other proteins, dyes, drugs or polymers.

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

This protocol details the important steps required for the bioconjugation of a cysteine containing protein to a maleimide, including reagent purification, reaction conditions, bioconjugate purification and bioconjugate characterization.

蛋白质生物缀合物的合成<em&gt;通过</em&gt;半胱氨酸马来酰亚胺化学

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the ...

Sulfate Separation by Selective Crystallization with a Bis-iminoguanidinium Ligand

A simple and effective method for selective sulfate separation from aqueous solutions by crystallization with a bis-guanidinium ligand, 1,4-benzene-bis(iminoguanidinium) (BBIG), is demonstrated. The ligand is synthesized as the chloride salt (BBIG-Cl) by in situ imine condensation of terephthalaldehyde with aminoguanidinium chloride in water, followed by crystallization as the sulfate salt (BBIG-SO4). Alternatively, BBIG-Cl is synthesized ex situ in larger scale from ethanol. The sulfate separation ability of the BBIG ligand is demonstrated by selective and quantitative crystallization of sulfate from seawater. The ligand can be recycled by neutralization of BBIG-SO4 with aqueous NaOH and crystallization of the neutral bis-iminoguanidine, which can be converted back into BBIG-Cl with aqueous HCl and reused in another separation cycle. Finally, 35S-labeled sulfate and &#946; liquid scintillation counting are employed for monitoring the sulfate concentration in solution. Overall, this protocol will instruct the user in the necessary skills to synthesize a ligand, employ it in the selective crystallization of sulfate from aqueous solutions, and quantify the separation efficiency.

A protocol for in situ aqueous synthesis of a bis(iminoguanidinium) ligand and its utilization in selective separation of sulfate is presented.

分离硫酸选择性结晶用双 -  iminoguanidinium配体

A simple and effective method for selective sulfate separation from aqueous solutions by crystallization with a bis-guanidinium ligand, ...

Electrophoretic Crystallization of Ultrathin High-performance Metal-organic Framework Membranes

We report the synthesis of thin, highly intergrown, polycrystalline metal-organic framework (MOF) membranes on a wide range of unmodified porous and non-porous supports (polymer, ceramic, metal, carbon, and graphene). We developed a novel crystallization technique, which is termed the ENACT approach: the electrophoretic nuclei assembly for the crystallization of highly intergrown thin films (ENACT). This approach allows for a high density of heterogeneous nucleation of MOFs on a chosen substrate via the electrophoretic deposition (EPD) directly from the precursor sol. The growth of well-packed MOF nuclei leads to a highly intergrown polycrystalline MOF film. We show that this simple approach can be used for the synthesis of thin, intergrown zeolite imidazole framework (ZIF)-7 and ZIF-8 films. The resulting 500 nm-thick ZIF-8 membranes show a considerably high H2 permeance (8.3 x 10-6 mol m-2 s-1 Pa-1) and ideal gas selectivities (7.3 for H2/CO2, 15.5 for H2/N2, 16.2 for H2/CH4, and 2655 for H2/C3H8). An attractive performance for C3H6/C3H8 separation is also achieved (a C3H6 permeance of 9.9 x 10-8 mol m-2 s-1 Pa-1 and a C3H6/C3H8 ideal selectivity of 31.6 at 25 &#176;C). Overall, the ENACT process, owing to its simplicity, can be extended to synthesize intergrown thin films of a wide range of nanoporous crystalline materials.

A simple, reproducible, and versatile approach for the synthesis of intergrown, polycrystalline metal-organic framework membranes on a wide range of unmodified porous and non-porous supports is presented.

超薄高性能金属-有机骨架膜的电泳结晶

We report the synthesis of thin, highly intergrown, polycrystalline metal-organic framework (MOF) membranes on a wide range of unmodified porous and ...

Solid-phase Synthesis of [4.4] Spirocyclic Oximes

A convenient synthetic route for spirocyclic heterocycles is well sought after due to the molecule&#39;s potential use in biological systems. By means of solid-phase synthesis, regenerating Michael (REM) linker strategies, and 1,3-dipolar cycloaddition, a library of structurally similar heterocycles, both with and without a spirocyclic center, can be constructed. The main advantages of the solid-support synthesis are as follows: first, each reaction step can be driven to completion using a large excess of reagents resulting in high yields; next, the use of commercially available starting materials and reagents keep the costs low; finally, the reaction steps are easy to purify via simple filtration. The REM linker strategy is attractive because of its recyclability and traceless nature. Once a reaction scheme is completed, the linker can be reused multiple times. In a typical solid-phase synthesis, the product contains either a part of or the whole linker, which can prove undesirable. The REM linker is &#34;traceless&#34; and the point of attachment between the product and the polymer is indistinguishable. The high diastereoselectivity of the intramolecular 1,3-dipolar cycloaddition is well documented. Limited by the insolubility of the solid support, the reaction progression can only be monitored by a change in the functional groups (if any) via infrared (IR) spectroscopy. Thus, the structural identification of intermediates cannot be characterized by conventional nuclear magnetic resonance (NMR) spectroscopy. Other limitations to this method stem from the compatibilities of the polymer/linker to the desired chemical reaction scheme. Herein we report a protocol that allows for the convenient production of spirocyclic heterocycles that, with simple modifications, can be automated with high-throughput techniques.

Here we present a protocol to demonstrate an efficient method for the synthesis of spirocyclic heterocycles. The five-step process utilizes solid-phase synthesis and regenerating Michael linker strategies. Generally difficult to synthesize, we present a customizable method for the synthesis of spirocyclic molecules otherwise inaccessible to other modern approaches.

[4.4] 刺环氧基的固相合成

A convenient synthetic route for spirocyclic heterocycles is well sought after due to the molecule&#39;s potential use in biological systems. By means of ...

半导体回转金属硫框架结晶的硫醇构建块的合成

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二碘化钐的制备和使用（SMI