Name: the synthesis, characterization and reactivity of a series of ruthenium n-triphosph complexes
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Description: Watch this Scientific Journal Video about The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes at JoVE.com

AP is grateful to Imperial College London for a PhD studentship via the Frankland Chair endowment. Johnson Matthey plc are also thanked for the loan of the precious metal salts used in this work.

注:进行所有合成在通风橱中，只有适当的安全问题已得到确认，并采取措施防止他们之后。个人防护装备，包括实验室外套，手套和护目镜，并应在任何时候都可以穿。 1.合成N，N，N-三（diphenylphosphinomethylene）胺，N（CH 2 PPH 2）3（N- -triphos PH）（1） <ol><li>向200ml的烘箱中干燥经由三个连续真空-氮气循环在双歧管的Schlenk线的Schlenk烧瓶中添加联苯（羟基亚甲基）氯化鏻11（6.99克，24.7毫摩尔），并置于氮气下。 </li><li>添加脱气的甲醇（30ml）和三乙胺（9.5毫升，68.1毫摩尔），并在RT搅拌1小时，以确保转化的鏻盐与hydroxymethene磷化氢。接着，在甲醇中加入脱气的氨水溶液（2M，4.1毫升，8.2毫摩尔）。 </li><li>在回流下2小时加热反应混合物，在此期间，将配体中沉淀出来，为白色固体。 </li><li>虽然N 个 -triphos 博士配位体是对氧化稳定的空气流过的时间很短，以获得最佳的纯度，通过套管26的过滤，除去溶剂在氮气氛下，并用脱气甲醇（3×10毫升）冲洗，得到分析纯的产物，并保存在氮气气氛下。 </li></ol> 2.合成的[Ru（CO）2 {N（CH 2 PPH 2）3}-κ3 P]（2） <ol><li>向200ml的烘箱干燥的Schlenk烧瓶中，在通过三个连续的真空-氮气循环加入正 -Triphos 博士 （1.0克，1.63毫摩尔）和〔茹3（CO）12]（347毫克，0.54毫摩尔），并置于氮气下双岐管的Schlenk线。 </li><li>加入30毫升无水，脱气的甲苯，并把混合物回流12小时。 </li><li>这12个小时的回流后，过滤通过套管将溶液至第二Schlenk烧瓶中，以除去反应过程中形成的少量的金属钌。 </li><li>使用双岐管的Schlenk线配有液氮冷却的捕集器，以诱导复合物的沉淀减少溶剂的体积到大约10毫升真空下。 </li><li>直至完全再溶解发生再结晶的沉淀物，通过加热轻轻（80-90℃）的油浴中，并随后缓慢冷却至RT通过从油浴中取出的热量，但是允许的Schlenk烧瓶中，以保持浸没。离开O / N，得到橙色结晶固体。 </li><li>隔离适于经由上清液到另一炉的套管过滤X射线衍射的橙色结晶干燥的Schlenk烧瓶中。接着，冲洗干燥和脱气的甲苯（2×5毫升）和干燥的真空 O / N的晶体。保存在一个单独的Schlenk烧瓶中的合并的上清液和洗液。 </li><li>从合并的上清液和漂洗溶液得到第二批晶体S按类似的再结晶过程中的步骤2.5和2.6，以提高反应的总产率。 </li><li>储存在氮气氛下的复杂的暴露于空气中会导致缓慢转化为氧化碳酸盐复合物（见下文）。 </li></ol> 3.合成的[Ru（CO 3）（CO）{N（CH 2 PPH 2）3}-κ3 P]（3） <ol><li>到200毫升的Schlenk烧瓶中，加入2（280毫克，0.364毫摩尔）和5毫升甲苯，以产生部分溶解的橙色悬浮液。 </li><li>插入连接于氧气进入悬浮液和气泡的氧气的气球的针在通过反应混合物持续10分钟的速率为每秒2-3气泡。 </li><li>为橙色沉淀物，通过过滤在空气中收集，并用甲苯（2×5ml）和乙醚（2×5毫升），并真空干燥，得到一种自由流动的橙色粉末，这是在空气中稳定。 </li><li>为了生长适合X-射线DIFFR晶体动作，通过缓慢地使该溶剂耗尽小瓶的侧溶解的3 100毫克的3ml二氯甲烷在顶部的小瓶和层3毫升甲苯。 <ol><li>离开这个O / N，得到结晶。通过倾析上清液，并洗涤该甲苯（2×3毫升）和乙醚（2×3毫升）隔离晶体。燥，真空在双歧管的Schlenk线。 </li></ol></li></ol> 4.合成的[Ru（H）2（CO）{N（CH 2 PPH 2）3}-κ3 P]（4） <ol><li>制备的3（763毫克，0.953毫摩尔）于20毫升无水的溶液，脱气THF中并在氮气正压（0.2巴）注入100ml高压釜工程师的高压反应器中。 </li><li>在反应器顶部空间气体改变为100％的氢气和加压到15巴，在室温，然后加热至100℃并搅拌2小时。 注意！确保所有安全程序已经坚持采用高时，压力系统！ </li><li>冷却至RT后，小心地排出过量的氢气在反应器液面上空间变为氮。 </li><li>将反应溶液转移至氮气下的100毫升的Schlenk烧瓶，并重新连接到双歧管的Schlenk线，滤波器通过套管后和稀释用20毫升无水，脱气甲醇。 </li><li>根据使用双岐管的Schlenk线装有一个液氮真空除去溶剂冷却阱，得到橙色粉末。用无水，脱气的甲醇（3×5毫升）和干燥的洗涤此橙色粉末，脱气乙醚（3×5毫升）和干燥的真空。 </li><li>生长适合X-射线衍射分析的晶体直径:/ N从4分层与无水的等体积量的饱和无水并脱气的甲苯溶液，脱气甲醇。 </li><li>储存在氮气氛下的复合物。 </li></ol> 5.反应〔期RuH 2（CO）{N（CH 2 PPH 2）3}-κ3 P]（4）用NH 4 PF 6和乙酰丙酸<ol><li>制备4在2ml无水的溶液（48.4毫克，65.2微摩尔），脱气的甲苯在炉中干燥的Schlenk烧瓶中，然后通过注射器添加的NH 4 PF 6的搅拌的溶液（10.6毫克，65.0微摩尔）在乙腈（2毫升）在一个单独的炉中干燥的Schlenk烧瓶中。 </li><li>在RT搅拌反应混合物2小时。之后，使用双岐管的Schlenk线配有液氮冷却的捕集器，得到中间体络合物[期RuH（CO）（MeCN中）{N（CH 2 PPH 2）3}-κ3 P]（除去溶剂，真空 5）。 </li><li>用干洗净，脱气己烷（3×3毫升）和干燥的真空分离络合物5，为棕色粉末。 </li><li>到的5在0.5ml中的溶液脱气丙酮-d 6，在0.5ml脱气丙酮-d 6的添加乙酰丙酸（10.8毫克，93.0微摩尔，1.43当量）。用2分钟搅拌反应混合物旋涡搅拌器。 </li><li>记录1 H和30 P {1 1 H}反应每小时16小时，观察反应NMR谱。27 </li></ol>

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The authors have nothing to disclose.

这里我们描述了高效的合成方法对于三齿膦配位体的合成和一系列钌配合物。 N 个 -triphos 博士配位体（1）可以高产率与一个简约的处理过程容易地制备。用于合成这些类型的配体的本磷基曼尼希反应是相当普遍的，并可以用于其它配位体的衍生物具有不同R基团上的P原子。10-12,15-18此外，这种合成方法是适合于在类似的碳为中心的三磷酸配位体，并且可以使用?...

钌膦基配合物是一些最广泛的研究和化学多功能分子催化剂。1-9典型地，这种钌催化剂包含决定了复杂的电子，空间相互作用，几何形状和溶解性或者单-或二齿配位体，并且其深刻地影响到催化活性。多齿膦系统已被广泛地少研究了催化，因为它们是公知的，由于多个磷供体在金属中心越大螯合效果与金属中心赋予更大的稳定性。这样的稳定​​可以是不希望的催化，然而，在更苛刻的反应条件下（较高的温度和压力下）这样的配体的配合物稳定性质可以是在确保催化剂完整性是有利的。我们10-12和13-18人已经调查传授复杂的稳定性和面部 COOR一个这样的多齿膦配体系统dination几何就是所谓 N- -triphos配体系列，其中3膦臂附着到心尖桥接氮原子形成一个潜在的三齿配体。其中一个主要的功能，以这些特定的配位体是容易的方式，它们可通过基于磷从容易得到的仲膦曼尼希反应（ 图1）来合成，因此，膦与各种R基团的，可以以高产率通常制备并以最少的工作了。这一方法的总的目标是提出一个浅显路线通过该钌配合物二氢化设有Ñ-triphos配体可用于随后的催化应用程序进行访问。最近，钌三磷酸基配合物已经引起注意，因为催化剂的衍生自生物质的产品，如乙酰丙酸，19,20生物酯11,21和二氧化碳22至更高的值的化学物质的氢化反应。将是有利展开属于任一，或比已报道，特别是如果它们是合成更容易访问，例如作为 N -triphos配位体的系统的更多活性钌三磷酸衍生物的范围。研究最多的碳为中心的模拟通常患有低产合成并涉及高度空气敏感金属磷化物的试剂，不同于N 个 -triphos配位体，这是更适应，更容易制备。10-18 Ñ-triphos配体保持相对不足的调查，只有钼，钨，钌，铑和金的复合物已报道从9出版物。与此形成鲜明对比的是硼碳为中心的类似物，为此，每年大约有50 900篇，分别以独特的化合物的大量。在亲手性烯烃23，我们在不对称催化加氢尽管如此，含有复合ñ-triphos发现应用程序LL的N作为不对称cyclohydroamination -protectedγ-丙二烯基磺酰胺。24此外，钌络合物由笨重Ñ-triphos配体具有磷杂配位部分的协调被认为激活硅烷，在有机硅化学的发展的关键步骤。25 由于在催化正在进行的研究项目的一部分，我们试图准备了一系列钌ñ-triphos 博士预催化剂，并研究它们的化学计量反应和催化潜力。尽管N 个 -triphos 博士最早被报道在25年前钼复合物，它们的应用，催化或以其他方式还没有被查处。这项工作表明N 个 -triphos支架，这尽管是普遍欠发达，拥有许多理想的特性，如复杂的稳定应用。在这里我们报告的合成路线和表征一系列钌Ñ-triphos 博士络合物可能会发现在催化氢化反应中的应用。

<table><tbody><tr><td>Methanol</td><td></td><td></td><td>Obtained from in-house solvent purification system: Innovative Technology, inc &quot;pure solv&quot; drying tower. Stored in ampules over activated molecular sieves under nitrogen.</td></tr><tr><td>Toluene</td><td></td><td></td><td></td></tr><tr><td>Diethyl Ether</td><td></td><td></td><td></td></tr><tr><td>Tetrahydrofuran (THF)</td><td></td><td></td><td></td></tr><tr><td>Acetonitrile</td><td></td><td></td><td></td></tr><tr><td>d&lt;sub&gt;6&lt;/sub&gt;-Acetone</td><td>VWR</td><td>VWRC87152.0011</td><td>Store in fridge</td></tr><tr><td>Triethylamine</td><td>Sigma-Aldrich</td><td>TO886-1L</td><td>Distilled and stored over activated molecular sieves under N&lt;sub&gt;2&lt;/sub&gt;</td></tr><tr><td>2 M Ammonia solution in methanol</td><td>Sigma-Aldrich</td><td>341428-100ML</td><td>Solution comes in a &quot;Sure-Seal&quot; bottle</td></tr><tr><td>NH&lt;sub&gt;4&lt;/sub&gt;PF&lt;sub&gt;6&lt;/sub&gt;</td><td>Sigma-Aldrich</td><td>216593-5G</td><td>Store in desiccator</td></tr><tr><td>Levulinic Acid</td><td>Acros Organics</td><td>125142500</td><td>Solid but melts close to room temperature</td></tr><tr><td>3 &amp;Aring; Molecular sieves</td><td>Alfa Aesar</td><td>LO5359</td><td>Activate by heating over night under vacuum</td></tr><tr><td>Schlenk flasks</td><td>GPE</td><td>Custom design</td><td></td></tr><tr><td>Dual-manifold Schlenk line</td><td>GPE</td><td>Custom design</td><td>Dual-manifold of i) N&lt;sub&gt;2&lt;/sub&gt; that has been passed through a silica drying column and ii) vacuum.</td></tr><tr><td>Rotary vacuum pump</td><td>Edwards</td><td>RV3 A652-01-903</td><td></td></tr><tr><td>100 ml Autoclave Engineer&#039;s high pressure reactor</td><td>Autoclave Engineer</td><td>Custon design</td><td></td></tr><tr><td>Vortex Stirrer</td><td>VWR</td><td>444-1378</td><td></td></tr></tbody></table>

the synthesis, characterization and reactivity of a series of ruthenium n-triphosph complexes

这里我们通过hydroxylmethylene膦前体与氨在氮气气氛下的磷基曼尼希反应在甲醇中报告一个三齿膦配位体N（CH 2 PPH 2）3（N- -triphos PH）（1）的合成。 N 个 -triphos 博士配体沉淀从溶液后约1小时回流，并可以分离，通过简单的过滤套管程序下，氮分析纯。在回流下N 个 -triphos 博士配体的[Ru 3（CO）12]的反应得到，显示CO气体对配体络合进化深红色溶液。复杂的[Ru（CO）2 {N（CH 2 PPH 2）3}-κ3 P]（2）中被隔绝在冷却至RT的橙色结晶。 31 P {1 1 H} NMR谱表明的特征单峰在较低频率相比于游离配体。的配合物2的甲苯溶液与氧气反应导致的碳酸盐配合物的[Ru（CO 3）（CO）{N（CH 2 PPH 2）3}-κ3 P〕瞬时沉淀（3），为空气稳定橙色固体。 3在15巴氢气在高压反应器中随后的氢化，得到二氢化物[期RuH 2（CO）{N（CH 2 PPH 2）3}-κ3 P]（4），将其充分利用X射线晶体学和核磁共振光谱。配合物3和4是潜在为一系列氢化反应，包括生物质衍生的产品，如乙酰丙酸（LA）的有用催化剂前体。配合物4被发现与干净的LA反应在质子源添加剂的存在的NH 4 PF 6，得到的[Ru（CO）{N（CH 2 PPH 2）3}-κ3 P {CH 3 CO（CH 2）2 CO 2 H}-κ2 O]（PF 6）（6）。

N个 -triphos 博士配位体（1）和钌配合物系列:钌（CO）2 {N（CH 2 PPH 2）3}-κ3 P]（2）中 ，使用[Ru（CO 3）（CO）{N （CH 2 PPH 2）3}-κ3 P]（3）和使用[Ru（H）2（CO）{N（CH 2 PPH 2）3}-κ3 P]（4）通过1 H组特征， 13 C <sup...

Watch this Scientific Journal Video about The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes at JoVE.com

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

钌膦配合物被广泛地用于均相催化反应，例如氢化反应。的一系列新的三齿钌配合轴承N个 -triphos配位体N（CH 2 PPH 2）3的合成的报道。另外，一个二氢化汝Ñ-triphos络合物与乙酰丙酸的化学计量反应进行说明。

一系列钌的合成，表征和反应<em&gt;Ñ</em&gt; -triphos<sup&gt;博士</sup&gt;配合

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the ...

the-synthesis-characterization-reactivity-series-ruthenium-n

Universidad San Sebastian

Research

JoVE Journal

Chemistry

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

12.1K 次观看.  Imperial College London. 钌膦配合物被广泛地用于均相催化反应，例如氢化反应。的一系列新的三齿钌配合轴承N个 -triphos配位体N（CH 2 PPH 2）3的合成的报道。另外，一个二氢化汝Ñ-triphos络合物与乙酰丙酸的化学计量反应进行说明。 

视频: The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions

Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family of easy accessible, very cheap, and air stable, but highly active and universally applicable C-C cross-coupling catalysts with an excellent functional group tolerance. Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1), the least stable complex within this series towards protons; e.g. in the form of water, allows an eased nanoparticle formation and hence, proved to be the most active Heck catalyst within this series at 100 &#176;C and is a very rare example of an effective and versatile catalyst system that efficiently operates under mild reaction conditions. Rapid and complete catalyst degradation under work-up conditions into phosphonates, piperidinium salts and other, palladium-containing decomposition products assure an easy separation of the coupling products from catalyst and ligands. The facile, cheap, and rapid synthesis of 1,1',1"-(phosphinetriyl)tripiperidine and 1 respectively, the simple and convenient use as well as its excellent catalytic performance in the Heck reaction at 100 &#176;C make 1 to one of the most attractive and greenest Heck catalysts available.
We provide here the visualized protocols for the ligand and catalyst syntheses as well as the reaction protocol for Heck reactions performed at 10 mmol scale at 100 &#176;C and show that this catalyst is suitable for its use in organic syntheses.

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions

Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1) is an easy accessible, cheap, and air stable, but highly active Heck catalyst with an excellent functional group tolerance that efficiently operates under mild reaction conditions to give the coupling products in very high yields.

Mizoroki-哎呀交叉偶联反应由二氯{双[1,1&#39;，1&#39;&#39;  - （phosphinetriyl）tripiperidine]}钯催化在温和的反应条件

Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family ...

科研

化学

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. Isonicotinic acid, or its derivatives, are coupled to variable length diaminoalkane chains under an inert atmosphere in anhydrous DMF or DMSO with the use of a weak base, triethylamine, and a coupling agent, 1-propylphosphonic anhydride. The products precipitate from solution upon formation or can be precipitated by the addition of water. If desired, the ligands can be further purified by recrystallization from hot water. Dinuclear platinum complex synthesis using the bispyridine ligands is done in hot water using transplatin. The most informative of the chemical characterization techniques to determine the structure and gross purity of both the bispyridine ligands and the final platinum complexes is 1H NMR with particular analysis of the aromatic region of the spectra (7-9 ppm). The platinum complexes have potential application as anticancer agents and the synthesis method can be modified to produce trinuclear and other multinuclear complexes with different hydrogen bonding functionality in the bridging ligand.

This protocol describes the use of amide coupling reactions of isonicotinic acid and diaminoalkanes to form bridging ligands suitable for use in the synthesis of multinuclear platinum complexes, which combine aspects of the anticancer drugs BBR3464 and picoplatin.

酰胺偶联反应为双吡啶基配体及其络合合成，以白金为双核抗癌药物

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. ...

Synthesis of a Water-soluble Metal&#8211;Organic Complex Array

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as Ru(II), Pt(II), and Rh(III). The compound, named as a water-soluble metal-organic complex array (WSMOCA), is obtained through 1) the conventional solution-chemistry-based preparation of the corresponding metal complex monomers having a 9-fluorenylmethyloxycarbonyl (Fmoc)-protected amino acid moiety and 2) their sequential coupling together with other water-soluble organic building units on the surface-functionalized polymeric resin by following the procedures originally developed for the solid-phase synthesis of polypeptides, with proper modifications. Traces of reactions determined by mass spectrometric analysis at the representative coupling steps in stage 2 confirm the selective construction of a predetermined sequence of metal centers along with the peptide backbone. The WSMOCA cleaved from the resin at the end of stage 2 has a certain level of solubility in aqueous media dependent on the pH value and/or salt content, which is useful for the purification of the compound.

A potential general method for the synthesis of water-soluble multimetallic peptidic arrays containing a predetermined sequence of metal centers is presented.

一个水溶性金属 - 有机络合物阵列合成

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as ...

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. Detailed and generalized protocols are also presented for testing the catalytic activity of such complexes in arylation and Suzuki-Miyaura cross-coupling reactions. Representative results are shown for the catalytic activity of the four complexes in arylation and Suzuki-Miyaura type reactions. For each of the reactions investigated, at least one of the four complexes successfully catalyzed the reaction, qualifying them as promising candidates for catalysis of many carbon-carbon bond-forming reactions. The protocols presented are general enough to be adapted for the synthesis, purification and catalytic activity testing of new palladium N-heterocyclic carbene complexes.

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. The complexes were tested for catalytic activity in arylation and Suzuki-Miyaura reactions. For each reaction investigated, at least one of the four complexes successfully catalyzed the reaction.

钯<em&gt;ñ</em&gt; - 杂环碳烯配合物:苯并咪唑盐的合成和碳 - 碳键合反应中的催化活性

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from ...

Synthesis and Evaluation of a Ruthenium-based Mitochondrial Calcium Uptake Inhibitor

We detail the synthesis and purification of a mitochondrial calcium uptake inhibitor, [(OH2)(NH3)4Ru(&#181;-O)Ru(NH3)4(OH2)]5+. The optimized synthesis of this compound commences from [Ru(NH3)5Cl]Cl2 in 1 M NH4OH in a closed container, yielding a green solution. Purification is accomplished with cation-exchange chromatography. This compound is characterized and verified to be pure by UV-vis and IR spectroscopy. The mitochondrial calcium uptake inhibitory properties are assessed in permeabilized HeLa cells by fluorescence spectroscopy.

A protocol for the synthesis, purification, and characterization of a ruthenium-based inhibitor of mitochondrial calcium uptake is presented. A procedure to evaluate its efficacy in permeabilized mammalian cells is demonstrated.

钌线粒体钙吸收抑制剂的合成与评价

We detail the synthesis and purification of a mitochondrial calcium uptake inhibitor, [(OH2)(NH3)4Ru(&#181;-O)Ru(NH3)4(OH2)]5+. The optimized synthesis of ...

Preparation of N-(2-alkoxyvinyl)sulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

Decomposition of N-tosyl-1,2,3-triazoles with rhodium(II) acetate dimer in the presence of alcohols forms synthetically versatile N-(2-alkoxyvinyl)sulfonamides, which react under a variety of conditions to afford useful N- and O-containing compounds. Acid-catalyzed addition of alcohols or thiols to N-(2-alkoxyvinyl)sulfonamide-containing phthalans provides access to ketals and thioketals, respectively. Selective reduction of the vinyl group in N-(2-alkoxyvinyl)sulfonamide-containing phthalans via hydrogenation yields the corresponding phthalan in good yield, whereas reduction with sodium bis(2-methoxyethoxy)aluminumhydride generates a ring-opened phenethylamine analogue. Because the N-(2-alkoxyvinyl)sulfonamide functional group is synthetically versatile, but often hydrolytically unstable, this protocol emphasizes key techniques in preparing, handling, and reacting these pivotal substrates in several useful transformations.

Preparation of N-2-alkoxyvinylsulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

Representative experimental procedures for the synthesis of N-(2-alkoxyvinyl)sulfonamides and subsequent conversion to phthalan and phenethylamine derivatives are presented in detail.

准备n-(2-alkoxyvinyl) 磺胺从n-tosyl-1,2,3-triazoles 和随后转换为取代 Phthalans 和 Phenethylamines

Decomposition of N-tosyl-1,2,3-triazoles with rhodium(II) acetate dimer in the presence of alcohols forms synthetically versatile ...

An In Vitro Enzymatic Assay to Measure Transcription Inhibition by Gallium(III) and H3 5,10,15-tris(pentafluorophenyl)corroles

Chemotherapy often involves broad-spectrum cytotoxic agents with many side effects and limited targeting. Corroles are a class of tetrapyrrolic macrocycles that exhibit differential cytostatic and cytotoxic properties in specific cell lines, depending on the identities of the chelated metal and functional groups. The unique behavior of functionalized corroles towards specific cell lines introduces the possibility of targeted chemotherapy.
Many anticancer drugs are evaluated by their ability to inhibit RNA transcription. Here we present a step-by-step protocol for RNA transcription in the presence of known and potential inhibitors. The evaluation of the RNA products of the transcription reaction by gel electrophoresis and UV-Vis spectroscopy provides information on inhibitive properties of potential anticancer drug candidates and, with modifications to the assay, more about their mechanism of action.
Little is known about the molecular mechanism of action of corrole cytotoxicity. In this experiment, we consider two corrole compounds: gallium(III) 5,10,15-(tris)pentafluorophenylcorrole (Ga(tpfc)) and freebase analogue 5,10,15-(tris)pentafluorophenylcorrole (tpfc). An RNA transcription assay was used to examine the inhibitive properties of the corroles. Five transcription reactions were prepared: DNA treated with Actinomycin D, triptolide, Ga(tpfc), tpfc at a [complex]:[template DNA base] ratio of 0.01, respectively, and an untreated control.
The transcription reactions were analyzed after 4 hr using agarose gel electrophoresis and UV-Vis spectroscopy. There is clear inhibition by Ga(tpfc), Actinomycin D, and triptolide.
This RNA transcription assay can be modified to provide more mechanistic detail by varying the concentrations of the anticancer complex, DNA, or polymerase enzyme, or by incubating the DNA or polymerase with the complexes prior to RNA transcription; these modifications would differentiate between an inhibition mechanism involving the DNA or the enzyme. Adding the complex after RNA transcription can be used to test whether the complexes degrade or hydrolyze the RNA. This assay can also be used to study additional anticancer candidates.

An In Vitro Enzymatic Assay to Measure Transcription Inhibition by GalliumIII and H3 5,10,15-trispentafluorophenylcorroles

Gallium(III) 5,10,15-(tris)pentafluorophenylcorrole and its freebase analogue exhibit low micromolar cell cytotoxicity. This manuscript describes an RNA transcription reaction, imaging RNA with an ethidium bromide-stained gel, and quantifying RNA with UV-Vis spectroscopy, in order to assess transcription inhibition by corroles and demonstrates a straightforward method of evaluating anticancer candidate properties.

一个<em&gt;在体外</em&gt;酶测定来测量转录抑制作用镓（Ⅲ）和H<sub&gt; 3</sub&gt; -5,10,15-三（五氟苯基）corroles

Chemotherapy often involves broad-spectrum cytotoxic agents with many side effects and limited targeting. Corroles are a class of tetrapyrrolic ...

生物工程

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction

A highly efficient transition metal catalyst removal method is developed. The water-soluble catalyst contains a newly-designed NHC ligand for the catalyst removal via host-guest interactions. The new NHC ligand possesses an adamantyl (guest) tethered linear ethylene glycol units for hydrophobic inclusion into the cavity of a &#946;-cyclodextrin (&#946;-CD) host compound. The new NHC ligand was applied to a Ru-based olefin metathesis catalyst. The Ru catalyst demonstrated excellent activity in representative ring-closing metathesis (RCM) and ring-opening metathesis polymerization (ROMP) reactions in aqueous media as well as organic solvent, CH2Cl2. After the reaction was complete, the lingering Ru residue was removed from the aqueous solution with the efficiency of more than 99% (53 ppm of Ru residue) by simple filtration utilizing a host-guest interaction between insoluble silica-grafted &#946;-CD (host) and the adamantyl moiety (guest) on the catalyst. The new Ru catalyst also demonstrated high removal efficiency via extraction when the reaction is run in organic solvent by partitioning the crude reaction mixture between layers of diethyl ether and water. In this way, the catalyst stays in aqueous layer only. In organic layer, the residual Ru amount was only 0.14 ppm in the RCM reactions of diallyl compounds.

A removable water-soluble N-heterocyclic carbene (NHC) ligand in aqueous media via host-guest interaction has been developed. We demonstrated representative olefin metathesis reactions in water as well as in dichloromethane. Via either host-guest interaction or extraction, the residual ruthenium (Ru) catalyst was as low as 0.14 ppm after the reaction.

水介质中水溶性钌烯烃置换催化剂的异质化去除与寄主交互作用

A highly efficient transition metal catalyst removal method is developed. The water-soluble catalyst contains a newly-designed NHC ligand for the catalyst ...

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

We report a method to generate the N-heterocyclic carbene (NHC) 1,3-dimesitylimidazol-2-ylidene (IMes) under UV-irradiation at 365 nm to characterize IMes and determine the corresponding photochemical mechanism. Then, we describe a protocol to perform ring-opening metathesis polymerization (ROMP) in solution and in miniemulsion using this NHC-photogenerating system. To photogenerate IMes, a system comprising 2-isopropylthioxanthone (ITX) as the sensitizer and 1,3-dimesitylimidazolium tetraphenylborate (IMesH+BPh4-) as the protected form of NHC is employed. IMesH+BPh4- can be obtained in a single step by anion exchange between 1,3-dimesitylimidazolium chloride and sodium tetraphenylborate. A real-time steady-state photolysis setup is described, which hints that the photochemical reaction proceeds in two consecutive steps: 1) ITX triplet is photo-reduced by the borate anion and 2) subsequent proton transfer takes place from the imidazolium cation to produce the expected NHC IMes. Two separate characterization protocols are implemented. Firstly, CS2 is added to the reaction media to evidence the photogeneration of NHC through formation of the IMes-CS2 adduct. Secondly, the amount of NHC released in situ is quantified using acid-base titration. The use of this NHC photo-generating system for the ROMP of norbornene is also discussed. In solution, a photopolymerization experiment is conducted by mixing ITX, IMesH+BPh4-, [RuCl2(p-cymene)]2 and norbornene in CH2Cl2, then irradiating the solution in a UV reactor. In a dispersed medium, a monomer miniemulsion is first formed then irradiated inside an annular reactor to produce a stable poly(norbornene) latex.

We describe a protocol to photogenerate N-heterocyclic carbenes (NHCs) by UV irradiation of a 2-isopropylthioxanthone/imidazolium tetraphenylborate salt system. Methods to characterize the photoreleased NHC and elucidate the photochemical mechanism are proposed. The protocols for ring-opening metathesis photopolymerization in solution and miniemulsion illustrate the potential of this 2-component NHC photogenerating system.

n-杂环卡本的光生成在光致环开环转移聚合中的应用

We report a method to generate the N-heterocyclic carbene (NHC) 1,3-dimesitylimidazol-2-ylidene (IMes) under UV-irradiation at 365 nm to characterize IMes ...

ARL Spectral Fitting as an Application to Augment Spectral Data via Franck-Condon Lineshape Analysis and Color Analysis

The ARL Spectral Fitting application provides a free, publicly accessible, and fully transparent method for performing Franck-Condon Lineshape Analysis (FCLSA) on spectral data, in addition to CIE color coordinate determination and basic spectral processing. While some of the features may be found in commercial software or in programs made by&#160;academic research groups, we believe that ARL Spectral Fitting is the only application that possesses all three of the aforementioned attributes.
This program is intended as a standalone, GUI-based application for use by an average laboratory researcher without requiring any coding knowledge or proprietary software. In addition to the standalone executable hosted on ARL GitHub, the associated MATLAB files are available for use and further development.
FCLSA augments the information found in luminescence spectra, providing meaningful insight into the relationship between the ground and excited states of a photoluminescent species. This insight is achieved by modeling spectra with two versions (modes) of an equation that are characterized by either four or six parameters, depending on which mode is used. Once optimized, the value of each of these parameters can be used to gain insight into the molecule, as well as to perform further analysis (for example, the free energy content of the excited-state molecule). This application provides tools for easy by-hand fitting of imported data, as well as two methods for optimizing this fit-damped least-squares fitting, powered by the Levenberg-Marquardt algorithm, and derivative-free fitting utilizing the Nelder-Mead simplex algorithm. Furthermore, estimations of sample color can be performed and reported in CIE and RGB coordinates.

This protocol introduces Franck-Condon Lineshape Analyses (FCLSA) of emission spectra and serves as a tutorial for the use of ARL Spectral Fitting software. The open-source software provides an easy and intuitive way to perform advanced analysis of emission spectra including excited state energy calculations, CIE color coordinate determination, and FCLSA.

ARL 光谱拟合作为通过 Franck-Condon 线形分析和颜色分析增强光谱数据的应用

The ARL Spectral Fitting application provides a free, publicly accessible, and fully transparent method for performing Franck-Condon Lineshape Analysis ...

一系列钌的合成，表征和反应

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Mizoroki-哎呀交叉偶联反应由二氯{双[1,1'，1'' - （phosphinetriyl）tripiperidine]}钯催化在温和的反应条件