我们感谢美国国家科学基金会（CHE0910597）和美国国立卫生研究院（P50-GM067982）为支持这项工作。我们非常感谢有益的讨论，关于荧光测量教授迈克尔·Trakselis的（匹兹堡大学）。我们承认克里斯蒂Gogick和罗宾·斯隆（匹兹堡大学），他们协助收集荧光数据。

1。微波辅助脱氢DA反应<ol><li>添加的对 - 氯苯乙烯衍生物（0.045克，0.18毫摩尔）和1,2 - 二氯乙烷（3毫升），以2-5毫升微波照射小瓶装有搅拌棒，以创建一个0.060 M溶液。这种浓度被使用，因为较高的浓度会导致形成不希望的产品。 </li><li>盖上盖子的的微波辐射小瓶，并将其放置在微波合成腔。 </li><li>照射该溶液在180℃下，在搅拌下与固定的保持时间为200分钟。保持时间是多长时间的照射下会出现在指定的温度。反应混合物会变成金黄色。较长的反应时间，是不利于反应的收率。 </li><li>确认反应完成后采用5％乙酸乙酯/己烷作为洗脱剂，用薄层色谱法（TLC）。可视化UV光的TLC板和高锰酸钾染色。的反应物的 R ft和产品，分别为0.2和0.25。 </li><li>转移反应，用1毫升的1,2 - 二氯乙烷中的闪烁瓶中冲洗的微波反应瓶中。这结果在约3毫升的闪烁小瓶中的溶液中。 </li><li>浓缩的闪烁小瓶的内容在40℃下在减压下用旋转蒸发器（10-30毫米汞柱）。蒸发的溶剂的，将需要5-10分钟，和45 mg将得到的粗制的褐色油。原油是稳定的，并可以无限期储存而不分解。 </li><li>纯化粗油状物通过硅胶吸移管，用5％乙酸乙酯/己烷作为洗脱剂，获得41毫克的富马酸二甲酯，为白色固体，通过过滤。 </li><li> 1 H核的磁共振（NMR）谱作为溶剂使用氘代氯仿（CDCl 3），该产品经确认的身份。对于一个300 MHz的NMR波谱仪，在萘的1 H NMR谱如下所示:7.80（四，J = 1.8赫兹，1H），7.72（四，J = 9.0赫兹，1H），7.70（，1H），7.38（西元，J = 1.8，9.0赫兹，1H），3.07（，J = 7.1赫兹吨，4H），2.66（3H），2.1​​8（P，J = 7.1赫兹，2H）ppm的。 </li></ol> 2。布赫瓦尔德哈特维希钯催化交叉偶联反应<ol><li>加入RuPhos钯化合物（3毫克，0.004毫摩尔），以烘箱干燥的0.5-2毫升Biotage公司微波照射小瓶装有搅拌棒和帽小瓶。 </li><li>疏散和笔芯小瓶用氮气三次通过刺穿隔垫的盖用小的针头。一旦清除的小瓶完成后，取出针。的微波照射小瓶将作为密封管中，在反应过程中，最好的结果是最小的空气是在反应容器中存在时获得。 </li><li>通过隔膜，锂，双（三甲基甲硅烷基）酰胺（0.32毫升的1.0M的THF溶液，0.32毫摩尔）在搅拌下，通过注射器添加。该解决方案将变成红色。 </li><li>搅拌2-10分钟后，加入焦（0.038克，0.16毫摩尔）在0.3毫升无水四氢呋喃（THF）通过注射器。可以使用附加的THF（高达0.2毫升），充分溶解的富马酸二甲酯。 </li><li>搅拌2-10分钟后，加入二甲胺（0.12毫升的2.0M的THF溶液，0.24毫摩尔），通过注射器，并降低反应容器到预热85℃油浴中。 </li><li>将反应混合物加热3小时，在85℃，或直至反应完成通过TLC。反应混合物的颜色是深褐色。对于薄层色谱法，利用20％乙酸乙酯/己烷溶液作为洗脱剂，并可视化用UV光所得到的板和高锰酸钾染色。反应物和产物的 R f分别是0.5和0.4。 </li><li>冷却反应至室温，取出小瓶帽，并用饱和氯化铵水溶液淬灭反应，（10毫升）。 </li><li>使用60毫升的分液漏斗中，从有机层中分离水层。萃取水层用乙酸乙酯萃取三次（12毫升）。 </li><li>在分液漏斗中，并合并有机层，用食盐水（15毫升）洗一次。 </li><li>硫酸钠干燥合并的有机层干燥10分钟，然后通过重力过滤除去硫酸钠。 </li><li>使用旋转蒸发器，所得的溶液在减压下浓缩，在30℃（10〜30毫米汞柱）。蒸发的溶剂的，将需要5-10分钟，和将得到粗制的褐色油。 </li><li>与一个1.5厘米的色谱柱和5％乙酸乙酯/己烷作为洗脱剂，通过硅胶柱色谱法纯化粗产物。的染料，将得到的黄色固体为27毫克。 </li><li>确认的身份的产品由1 H NMR光谱使用CDCl 3作为溶剂。对于一个400 MHz的NMR光谱仪，1 H NMR谱的染料如下:7.64（D，J = 9.0赫兹，1H），7.56（，1H），7.11（，J = 2.5，9.0赫兹，1H西元），6.87（D，J = 2.5赫兹，1H），3.02（6H），3.02 - 2.87（4H），2.65（3H），2.12（P，J = 7.3赫兹，2H）ppm的。 </li></ol> 3。制备染料溶液中的光物理研究<ol><li> 1毫克的染料转移到一个干净的，干燥的10毫升容量瓶中，并稀释至体积用二氯甲烷（DCM），得到了0.4×10 -3 M的储备溶液的染料。 </li><li>第二个10 mL容量瓶中，稀释的原液253μl的准备1×10 -5 M解决方案的染料量与DCM。此解决方案将被用于收集的UV-Vis和染料的荧光数据。 </li></ol> 4。紫外 - 可见吸收光谱<ol><li>填写两个石英分光光度计细胞与DCM。这些都是空白样品。把它们放入紫外 - 可见分光光度计腔。切勿接触光学器件表面的细胞。处理细胞的侧面板的顶部，不面对光轴。 </li><li>设置仪器参数的狭缝宽度为2和采集速率为480nm /分钟。选择样品的名称，并选择收购的范围从600到200纳米。 </li><li>收集背景的光谱，从仪器中取出样品细胞，把它倒空，然后用清水冲洗1×10 -5 M染料溶液灌装前的几个部分。避免溢出细胞。在插入样品细胞放回持有人之前，用干净的镜头纸仔细擦拭牢房窗户。 </li><li>收集样品的吸收光谱。观察到的最大吸收波长为377 nm。 </li><li>仔细清洁石英与水，丙酮，乙醇，然后再运行分析其他样品的UV-Vis吸收分光光度计细胞。 </li><li>使用Excel或Origin软件绘制和分析收集到的数据。 </li></ol> 5。荧光发射光谱<ol><li>填充石英的1×10 -5 M染料溶液的荧光细胞，并将其放置到spectrofluoromet呃。避免与皮肤接触的光学表面的细胞。 </li><li>设置仪器参数:激发波长为334 nm处，狭缝宽度为2，以0.1nm /秒的采集速率，采集范围从390至750纳米。甲390 nm的切口过滤器需要以除去散射光从发射源。 </li><li>收集的样品的荧光发射光谱。观察到在510 nm处的荧光发射最大值。 </li><li>清洁的石英荧光细胞与水，丙酮，和乙醇在运行前对其它样品的荧光分析。 </li><li>使用Excel或Origin软件绘制和分析收集到的数据。 </li></ol>

<ol>
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作者宣称，他们没有竞争的金融利益。

微波辅助脱氢DA反应 DA反应的分子内脱氢，苯乙烯基前体的微波辐射（MWI）在71-100％的高收益率和较短的反应时间产生不同的萘结构，需要短短的30分钟（ 图1）18。最困难的方面的进行脱氢DA反应是溶剂的选择，这往往是复杂的，因为需要考虑到各种溶剂的特性，以确保最佳的加热。第一和最重要的是，一个成功的反应必须有可能在溶剂中，是与微波条件兼?...

小分子设计和合成一系列的科学领域，包括医药，农药，有机染料和多1的发展是至关重要的。 （DDA）的Diels-Alder（DA）和脱氢的Diels-Alder反应是在小的环状和芳族化合物2-4的合成，尤其是强大的工具。此外，热脱氢DA反应苯乙烯二烯，炔烃的亲二烯体的芳族化合物的合成提供了一种潜在的有利的路线通过初步形成双环[2.2.2]辛烯酮类化合物，可以进一步在氧化条件下芳香5。通过采用分子内的热脱氢DA苯乙烯二烯与炔反应，利用苯乙烯作为二烯，如不需要的[2 +2]环加成5,6和聚合反应7和区域选择性差，减轻和萘化合物的问题通常与可以生成。 苯乙烯与炔烃分子内的热脱氢DA反应也不是没有相当大的问题。首先，大多数反应受到产量低，长的反应时间，和高的反应温度8-11。此外，很多反应不提倡纯形成的萘产品，萘和二氢生产，往往分不开的混合物通过柱层析11,12。的前体的苯乙烯 - ynes系绳也仅限于包括的杂原子和/或羰基部分。仅是一个示例报告所有含碳的系绳，要求的条件为250℃下48小时整洁，以便取得萘生成10。 除了有限的各种内的系绳的起始原料，这种方法的最严重的限制之一是在常规的热条件下的耐受性的功能的缺乏。的炔末端的原料或者是未取代的或附加的苯基或三甲基甲硅烷基（TMS）基团8-13。 在一个实例中，示出在炔烃末端酯进行脱氢的DA反应，但这个结果萘，二氢萘产品11的混合物中。后来的提案建议，TMS组附加炔末端是必要的，实现独家萘形成的高收益率10。 热脱氢DA反应报告的各种功能的不足，严重限制了潜在的这种反应对装配独特的萘结构。 萘结构的变化源于它们的功能，在多个科学领域，特别是有机荧光染料14,15的小分子构建模块的愿望。出色的空间分辨率和响应时间的小组织ANIC染料监测实时事件16已经导致数百市售的荧光化合物的发展。许多这些染料是萘与分立的光物理和化学性质15。 选择的荧光染料具有特殊性能的监视单个的功能，从而导致不​​断增长的需求提供更多样化的光物理性质的荧光基团为新的类是具有挑战性的。为此目的，热分子内脱氢DA反应的苯乙烯与炔烃，允许多样化的一个独特的萘骨架将是潜在的有利开发新的萘的含有荧光染料中的应用。 作为一种替代方法，常规加热，微波辅助化学是有利的，因为它提供的化学样品的更均匀的加热，从而导致更高的化学产率，更快的反应速率，温和的反应条件下s，而往往是不同的选择性的产品17。 采用微波辅助与传统加热条件下的反应时间从几天减少到几分钟，增加以前差收益，降低反应温度，并提供更多的选择性形成的分子内的苯乙烯脱氢DA反应，消除的方法与此相关的问题所需的富马酸二甲酯产物。微波辅助的反应条件下，也可能会更容易，更多样化的功能，以方便将进入富马酸二甲酯的产品，这是前所未有的。只有一个现有的例子已被报道利用脱氢DA的反应，其中的90％产率的富马酸二甲酯和二氢化萘中得到尽可能少为15分钟，在170°C 12的微波辅助的条件。 在这里报道了微波辅助分子内脱氢酶本地DA反应的苯乙烯基衍生工具的专属形成的官能化和多样化的富马酸二甲酯的产品，在短短的30分钟，高定量的产率18。此协议进一步证明该实用程序的萘产品的一个步骤转换成一种新型的溶致变色荧光染料的光物理性质的对手流行的商用染料普罗丹19。

<table><tbody><tr><td colspan="4">&lt;strong&gt;Reagent/Material&lt;/strong&gt;</td></tr><tr><td>1,2-Dichlor&amp;#8211;thane, ACS reagent &amp;#8805;99.0% </td><td>Sigma-Aldrich</td><td>319929</td><td></td></tr><tr><td>SiliaPlate G TLC - glass-backed, 250 &amp;mu;m</td><td>Silicycle</td><td>TLG-R10011B-323</td><td></td></tr><tr><td>Ethyl acetate, certified ACS &amp;#8805;99.5%</td><td>Fisher Scientific</td><td>E14520</td><td></td></tr><tr><td>Hexanes, certified ACS &amp;#8805;98.5%</td><td>Fisher Scientific</td><td>H29220</td><td></td></tr><tr><td>Silica gel, standard grade</td><td>Sorbent Technologies</td><td>30930M</td><td>60 A, 40-63 &amp;mu;M (230 x 400 mesh)</td></tr><tr><td>RuPhos palladacycle</td><td>Strem</td><td>46-0266</td><td></td></tr><tr><td>Nitrogen gas</td><td>Matheson TRIGAS</td><td>NI304</td><td>Nitrogen 304cf, industrial</td></tr><tr><td>Lithium bis(trimethylsilyl) amide solution</td><td>Sigma-Aldrich</td><td>225770</td><td>1.0 M solution in THF</td></tr><tr><td>Tetrahydrofuran anhydrous &amp;#8805;99.9%</td><td>Sigma-Aldrich</td><td>401757</td><td>Inhibitor-free</td></tr><tr><td>Dimethylamine solution</td><td>Sigma-Aldrich</td><td>391956</td><td>2.0 M solution in THF</td></tr><tr><td>Ammonium chloride</td><td>Fisher Scientific</td><td>A661-500</td><td></td></tr><tr><td>Sodium sulfate, anhydrous (granular)</td><td>Fisher Scientific</td><td>S421-500</td><td></td></tr><tr><td>Chromatography column</td><td>Chemglass</td><td>CG-1188-04</td><td>&amp;#189; in ID x 18in E.L.</td></tr><tr><td>Cyclohexane, &amp;#8805;99.0%</td><td>Fisher Scientific</td><td>C556-1</td><td></td></tr><tr><td>Toluene anhydrous, 99.8%</td><td>Sigma-Aldrich</td><td>24451</td><td></td></tr><tr><td>1,4-Dioxane anhydrous, 99.8%</td><td>Sigma-Aldrich</td><td>296309</td><td></td></tr><tr><td>Tetrahydrofuran anhydrous, &amp;#8805;99.9%</td><td>Sigma-Aldrich</td><td>186562</td><td>250 ppm BHT as inhibitor</td></tr><tr><td>Dichloromethane</td><td>Sigma-Aldrich</td><td>650463</td><td>Chromasolv Plus</td></tr><tr><td>Chloroform, &amp;#8805;99.8%</td><td>Fisher Scientific</td><td>C298-1</td><td></td></tr><tr><td>Acetonitrile anhydrous, 99.8%</td><td>Sigma-Aldrich</td><td>271004</td><td></td></tr><tr><td>Dimethyl sulfoxide, &amp;#8805;99.9%</td><td>Fisher Scientific</td><td>D128</td><td></td></tr><tr><td>Ethyl alcohol </td><td>Pharmco-AAPER</td><td>11ACS200</td><td>Absolute</td></tr><tr><td colspan="4">&lt;strong&gt;Equipment&lt;/strong&gt;</td></tr><tr><td>Microwave Synthesizer</td><td>Biotage</td><td>Biotage Initiator Exp</td><td></td></tr><tr><td>Microwave Vial</td><td>Biotage</td><td>352016</td><td>0.5 &amp;#8211; 2 ml</td></tr><tr><td>Microwave Vial</td><td>Biotage</td><td>351521</td><td>2 &amp;#8211; 5 ml</td></tr><tr><td>Microwave Vial Cap</td><td>Biotage</td><td>352298</td><td></td></tr><tr><td>Microwave Synthesizer</td><td>Anton Paar</td><td>Monowave 300</td><td></td></tr><tr><td>Microwave Vial G4</td><td>Anton Paar</td><td>99135</td><td></td></tr><tr><td>Microwave Vial Cap</td><td>Anton Paar</td><td>88882</td><td></td></tr><tr><td>NMR Spectrometer</td><td>Bruker</td><td>Avance</td><td>300 or 400 MHz</td></tr><tr><td>UV-Visible Spectrometer</td><td>PerkinElmer</td><td>Lamda 9</td><td></td></tr><tr><td>Spectrophotometer cell</td><td>Starna Cells</td><td>29B-Q-10</td><td>Spectrosil quartz, path length 10 mm, semi-micro, black wall</td></tr><tr><td>Spectrofluorometer </td><td>HORIBA Jobin Yvon</td><td>FluoroMax-3 S4</td><td></td></tr><tr><td>Fluorometer cell</td><td>Starna Cells</td><td>29F-Q-10</td><td>Spectrosil quartz, path length 10 mm, semi-micro</td></tr></tbody></table>

microwave-assisted intramolecular dehydrogenative diels-alder reactions for the synthesis of functionalized naphthalenes/solvatochromic dyes

功能化萘的应用程序在不同的研究领域，从天然或生物活性分子的合成新型有机染料的制备。虽然众多的策略已被报告给访问萘棚架，许多程序在结合功能，这反过来又变窄的范围内可用的基板方面仍然存在局限性。因此，通用的方法直接访问取代的萘的发展是非常必要的。 的Diels-Alder（DA）的环加成反应是一个强大的和有吸引力的方法，从容易得到的起始原料，形成饱和的和不饱和的环系统。本文描述一种新的微波辅助分子内脱氢DA反应的苯乙烯基衍生物生成多种官能化的环戊二烯并[b]萘，无法使用现有的合成方法来制备第当比常规加热，微波辐射加速反应速率，提高产量，并限制了不希望的副产物的形成。 此协议的实用程序进一步证明由转换的DA环加成到一种新型的溶致变色荧光染料经由布赫瓦尔德-哈特威格钯催化的交叉偶联反应。荧光光谱法，作为一个信息和灵敏的分析技术，研究领域包括环境科学，医学，药理学，细胞生物学中起着关键的作用。获得各种新的有机荧光团所提供的微波辅助的脱氢DA反应允许在这些领域的进一步提高。

照射微波（MWI）的苯乙烯基衍生物，在180℃结果完全环戊二烯并[b]萘形成在低至30分钟，并在高至定量的产率（ 图1）18。 无二氢萘副产品是观察，并通过1 H NMR光谱的产品，而不需要额外的纯化照射后（ 图2）出现纯。耐受性良好的富马酸二甲酯框架的各种变化利用这些热的条件下，包括该系绳的变化和替代图案的萘环，吸电子基团的一个?...

Watch this Scientific Journal Video about Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes at JoVE.com

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes

微波辅助分子内的脱氢的Diels-Alder反应（DA）提供简洁的访问功能化环戊[<em&gt; B</em&gt;]萘积木。一个步骤转换成脱氢DA双环[2.2.2]辛烯酮类化合物的新型溶致变色荧光染料通过布赫瓦尔德-哈特维希钯催化交叉偶联反应证明了这种方法的效用。

微波辅助分子内Diels-Alder反应的功能化萘/变色染料的合成脱氢

Functionalized naphthalenes have applications in a variety of research fields ranging from the synthesis of natural or biologically active molecules to ...

microwave-assisted-intramolecular-dehydrogenative-diels-alder

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Organic Chemistry

Chemistry

Unit 1

Dienes, Conjugated Pi Systems, and Pericyclic Reactions

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16.9K 次观看.  University of Pittsburgh. 微波辅助分子内的脱氢的Diels-Alder反应（DA）提供简洁的访问功能化环戊[ B]萘积木。一个步骤转换成脱氢DA双环[2.2.2]辛烯酮类化合物的新型溶致变色荧光染料通过布赫瓦尔德-哈特维希钯催化交叉偶联反应证明了这种方法的效用。

视频: Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides (CHIPS)

The direct functionalization of C-H bonds is an important and long standing goal in organic chemistry. Such transformations can be very powerful in order to streamline synthesis by saving steps, time and material compared to conventional methods that require the introduction and removal of activating or directing groups. Therefore, the functionalization of C-H bonds is also attractive for green chemistry. Under oxidative conditions, two C-H bonds or one C-H and one heteroatom-H bond can be transformed to C-C and C-heteroatom bonds, respectively. Often these oxidative coupling reactions require synthetic oxidants, expensive catalysts or high temperatures. Here, we describe a two-step procedure to functionalize indole derivatives, more specifically tetrahydrocarbazoles, by C-H amination using only elemental oxygen as oxidant. The reaction uses the principle of C-H functionalization via Intermediate PeroxideS (CHIPS). In the first step, a hydroperoxide is generated oxidatively using visible light, a photosensitizer and elemental oxygen. In the second step, the N-nucleophile, an aniline, is introduced by Br&#248;nsted-acid catalyzed activation of the hydroperoxide leaving group. The products of the first and second step often precipitate and can be conveniently filtered off. The synthesis of a biologically active compound is shown.

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

A two-step procedure for the synthesis of pharmaceutically active indole-derivatives by C-H functionalization with anilines is described, using photo- and Br&#248;nsted acid catalysis.

通过中级过氧化物的抗病毒四氢咔唑衍生物的合成光化学和酸催化CH官能（筹）

The direct functionalization of C-H bonds is an important and long standing goal in organic chemistry. Such transformations can be very powerful in order ...

科研

化学

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these challenges.

功能化的合成与表征金属 - 有机骨架

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

Highly Stereoselective Synthesis of 1,6-Ketoesters Mediated by Ionic Liquids: A Three-component Reaction Enabling Rapid Access to a New Class of Low Molecular Weight Gelators

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form catalytically active N-Heterocyclic Carbenes (NHCs). Here we have used ILs as precatalysts in the addition of &#945;,&#946;-unsaturated aldehydes to chalcones to form 1,6-ketoesters, incorporating an anti-diphenyl moiety in a highly stereoselective fashion. The reaction has a broad substrate scope and several functional groups and heteroaromatics can be integrated into the ketoester backbone in generally good yields with maintained stereoselectivity. The reaction protocol is robust and scalable. The starting materials are inexpensive and the products can be obtained after simple filtration, avoiding solvent-demanding chromatography. Furthermore, the IL can be recycled up to 5 times without any loss of reactivity. Moreover, the 1,6-ketoester end product is a potent gelator in several hydrocarbon based solvents. The method enables rapid access to and evaluation of a new class of low molecular weight gelators (LMWGs) from recyclable and inexpensive starting materials.

Ionic liquids (ILs) mediate fast, simple and cheap access to 1,6-ketoesters in high diastereoselectivities and good yields. The reaction protocol is robust and the 1,6-ketoesters can be obtained in gram scale after a simple filtration protocol. Moreover, the 1,6-ketoesters are potent gelators in hydrocarbon solvents.

1,6-酮酯高立体选择性合成离子液体介导:三组分反应启用快速进入低分子量胶凝剂的新型类

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form ...

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

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 glycosyl donor. Following azido-nitration of a glycal, the product 2-azido-1-nitrate ester can be hydrolyzed under microwave-assisted irradiation. This transformation is usually achieved using strongly nucleophilic reagents and extended reaction times. Microwave irradiation induces hydrolysis, in the absence of reagents, with short reaction times. Following denitration, the intermediate anomeric alcohol is converted, in the same pot, to the corresponding 2-azido-1-trichloroacetimidate.

A 2-azido-1-nitrate-ester can be converted to the corresponding 2-azido-1-trichloroacetimidate in a one-pot procedure. The goal of the manuscript is to demonstrate utility of the microwave reactor in carbohydrate synthesis.

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

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 ...

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 ...

Microwave-Assisted Preparation of 1-Aryl-1H-pyrazole-5-amines

A synthetic process for the preparation of a variety of 1-aryl-1H-pyrazole-5-amines was developed. The microwave-mediated nature of this method makes it efficient in both time and resources and utilizes water as the solvent. 3-Aminocrotononitrile or an appropriate &#945;-cyanoketone is combined with an aryl hydrazine and dissolved in 1 M HCl. The mixture is then heated in a microwave reactor at 150 &#176;C, typically for 10-15 min. The product can be readily obtained by basifying the solution with 10% NaOH and isolating the desired compound with a simple vacuum filtration. The use of water as a solvent in this reaction lends to its ease and utility in production, and this method is easily reproducible with a variety of functional groups. Typical isolated yields range from 70-90%, and reactions can be performed on the milligram to gram scale with little to no change in observed yields. Some of the applications of these molecules and their derivatives include pesticides, anti-malarials, and chemotherapeutics, among many others.

Microwave-Assisted Preparation of 1-Aryl-1H-pyrazole-5-amines

1-Aryl-1H-pyrazole-5-amines are prepared from aryl hydrazines combined with either 3-aminocrotononitrile or an &#945;-cyanoketone in a 1 M HCl solution using a microwave reactor. Most reactions are done in 10-15 minutes and pure product can be obtained via vacuum filtration with typical isolated yields of 70-90%.

微波辅助制备1-Aryl-1 H-pyrazole-5胺

A synthetic process for the preparation of a variety of 1-aryl-1H-pyrazole-5-amines was developed. The microwave-mediated nature of this method makes it ...

A Direct, Regioselective and Atom-Economical Synthesis of 3-Aroyl-N-hydroxy-5-nitroindoles by Cycloaddition of 4-Nitronitrosobenzene with Alkynones

We introduced a regioselective and atom-economical procedure for the synthesis of 3-substituted indoles by annulation of nitrosoarenes with ethynyl ketones. The reactions were carried out achieving indoles without any catalyst and with excellent regioselectivity. No traces of 2-aroylindole products were detected. Working with 4-nitronitrosobenzene as starting material, the 3-aroyl-N-hydroxy-5-nitroindole products precipitated from the reaction mixtures and were isolated by filtration without any further purification technique. Differently from the corresponding N-hydroxy-3-aryl indoles that, spontaneously in solution, give dehydrodimerization products, the N-hydroxy-3-aroyl indoles are stable and no dimerization compounds were observed.

A Direct, Regioselective and Atom-Economical Synthesis of 3-Aroyl-N-hydroxy-5-nitroindoles by Cycloaddition of 4-Nitronitrosobenzene with Alkynones

3-Aroyl-N-hydroxy-5-nitroindoles were synthesized by cycloaddition of 4-nitronitrosobenzene with a conjugated terminal alkynone in a one-step thermal procedure. Preparation of the nitrosoarene and of the alkynones were adequately reported and respectively through oxidation procedures on the corresponding aniline and on the alkynol.

A 直接、再生和原子经济合成3-Aroyl-N-羟基-5-硝基胺基，通过环加4-硝基苯与烷基诺

We introduced a regioselective and atom-economical procedure for the synthesis of 3-substituted indoles by annulation of nitrosoarenes with ethynyl ...

A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis

Heteroarylation introduces heteroaryl fragments to organic molecules. Despite the numerous available reactions reported for arylation via transition metal catalysis, the literature on direct heteroarylation is scarce. The presence of heteroatoms such as nitrogen, sulfur and oxygen often make heteroarylation a challenging research field due to catalyst poisoning, product decomposition and the rest. This protocol details a highly efficient direct &#945;-C(sp3) heteroarylation of ketones under microwave irradiation. Key factors for successful heteroarylation include the use of XPhos Palladacycle Gen. 4 Catalyst, excess base to suppress side reactions and the high temperature and pressure achieved in a sealed reaction vial under microwave irradiation. The heteroarylation compounds prepared by this method were fully characterized by proton nuclear magnetic resonance spectroscopy (1H NMR), carbon nuclear magnetic resonance spectroscopy (13C NMR) and high-resolution mass spectrometry (HRMS). This methodology has several advantages over literature precedents including broad substrate scope, rapid reaction time, greener procedure and operational simplicity by eliminating the preparation of intermediates such as silyl enol ether. Possible applications for this protocol include, but are not limited to, diversity-oriented synthesis for the discovery of biologically active small molecules, domino synthesis for the preparation of natural products and ligand development for new transition metal catalytic systems.

Heteroaryl compounds are important molecules utilized in organic synthesis, medicinal and biological chemistry. A microwave-assisted heteroarylation using palladium catalysis provides a rapid and efficient method to attach heteroaryl moieties directly to ketone substrates.

利用过渡金属催化的酮的微波辅助直接异化

Heteroarylation introduces heteroaryl fragments to organic molecules. Despite the numerous available reactions reported for arylation via transition metal ...

Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions

The interest on nitrogen-containing heterocycles has expanded rapidly in the synthetic community since they are important motifs for new drugs. Traditionally, they were synthesized through thermal cycloaddition reactions, whereas today, photocatalysis is preferred due to the mild and efficient conditions. With this focus, a new photocatalytic method for the synthesis of nitrogen-containing heterocycles is highly desired. Here, we report a protocol for the biosynthesis of cercosporin, which could function as a metal-free photocatalyst. We then illustrate cercosporin-photocatalyzed protocols for the synthesis of nitrogen-containing heterocycles 1,2,3-thiadiazoles through annulation of azoalkenes with KSCN, and synthesis of 1,4,5,6-tetrahydropyridazines [4+2] through cyclodimerization of azoalkenes under mild conditions, respectively. As a result, there is a new bridge between the microbial fermentation method and organic synthesis in a mild, cost-effective, environmentally friendly and sustainable manner.

New routes for the synthesis of nitrogen-containing heterocycles utilizing cercosporin as a metal-free photocatalyst were developed.

神经素-光催化 [4]1]- 和 [4]2]- 在轻度条件下对阿佐尔克内斯的无效

The interest on nitrogen-containing heterocycles has expanded rapidly in the synthetic community since they are important motifs for new drugs. ...

Synthesis of pH Dependent Pyrazole, Imidazole, and Isoindolone Dipyrrinone Fluorophores using a Claisen-Schmidt Condensation Approach

Methine-bridged conjugated bicyclic aromatic compounds are common constituents of a range of biologically relevant molecules such as porphyrins, dipyrrinones, and pharmaceuticals. Additionally, restricted rotation of these systems often results in highly to moderately fluorescent systems as observed in 3H,5H-dipyrrolo[1,2-c:2',1'-f]pyrimidin-3-ones, xanthoglows, pyrroloindolizinedione analogs, BODIPY analogs, and the phenolic and imidazolinone ring systems of Green Fluorescent Protein (GFP). This manuscript describes an inexpensive and operationally simple method of performing a Claisen-Schmidt condensation to generate a series of fluorescent pH dependent pyrazole/imidazole/isoindolone dipyrrinone analogs. While the methodology illustrates the synthesis of dipyrrinone analogs, it can be translated to produce a wide range of conjugated bicyclic aromatic compounds. The Claisen-Schmidt condensation reaction utilized in this method is limited in scope to nucleophiles and electrophiles that are enolizable under basic conditions (nucleophile component) and non-enolizable aldehydes (electrophile component). Additionally, both the nucleophilic and electrophilic reactants must contain functional groups that will not inadvertently react with hydroxide. Despite these limitations, this methodology offers access to completely novel systems that can be employed as biological or molecular probes.

The Claisen-Schmidt condensation reaction is an important methodology for the generation of methine-bridged conjugated bicyclic aromatic compounds. Through utilizing a base-mediated variant of the aldol reaction, a range of fluorescent and/or biologically relevant molecules can be accessed through a generally inexpensive and operationally simple synthetic approach.