我们承认药学院（悉尼大学），Erciyes大学研究基金和TUBITAK（1059B141400496）的财务支持。我们感谢Tim Harland（悉尼大学）编辑视频。

注意:使用许多挥发性溶剂作为下面详述的方案的一部分，以便在工作通风橱中进行所有实验。在使用前请穿戴适当的个人防护装备，并咨询各试剂的MSDS;在此提供有关危险试剂和步骤的简要信息。 苯并咪唑盐的合成和纯化（化合物1-4） <ol><li>立即将100mL Schlenk管夹紧，并将搅拌棒，1mmol苯并咪唑，1mmol氢氧化钾和60mL乙醇作为溶剂。 注意:氢氧化钾可能有害。避免吸入灰尘并远离水分。 注意:乙醇易挥发和易燃。远离明火或点火源。 注意:如果没有氢氧化钾，可以使用氢氧化钠。咨询在进行此建议修改前，请先进行氢氧化钠的MSDS。 </li><li>将Schlenk管放入油浴中，以在搅拌步骤中均匀和安全地加热反应混合物。将管连接到冷凝器，以防止搅拌过程中溶剂蒸发。确保玻璃配件部分已充分润滑且安装正确。 </li><li>将反应混合物在25℃下搅拌1小时，以使所有固体完全溶解，以及在苯并咪唑分子中破坏氮 - 氢键。 注意:使用冷凝器进行该搅拌步骤并不是必需的，但是由于在下面的步骤1.5中必须使用冷凝器进行回流，所以在此步骤中可以方便地安装冷凝器，并将其用于两个步骤。否则，该步骤可以通过用带油的塞子密封Schlenk管来进行。 </li><li> 1小时后，从冷凝器中取出Schlenk管，并缓慢加入1mmol所选择的a卤化物至混合物。 注意:芳基卤化物是刺激物，可能是有害的。在进行之前，请咨询相关MSDS。 </li><li>将Schlenk管重新连接到冷凝器，并将混合物在78℃（接近乙醇沸点）下回流6小时，以使反应达到完成。让混合物在回流结束后冷却至25℃。 </li><li>从冷凝器中取出Schlenk管，并使用一些纸巾擦拭管口的油脂。然后，使用漏斗和滤纸过滤反应混合物以除去反应期间形成的氯化钾沉淀。在烧杯中收集滤液。 </li><li>将含有N-烷基苯并咪唑产物的滤液转移到干净的Schlenk管中。用油脂塞子密封管，并用真空除去滤液中的乙醇溶剂。 注意:对于协议中的所有步骤使用中等强度的真空以及连接真空的管的轻微和连续的振动。 </li><li>一旦除去所有溶剂，开启Schlenk管，加入5 mL乙醚洗涤留下的N-烷基苯并咪唑产物。轻轻摇动管子进行洗涤。 <ol><li>洗完后，用一些纸巾擦拭管子的嘴唇上的油脂，并将乙醚倒入烧杯中。重复此洗涤步骤几次，加入5 mL乙醚，每次滗析。 注意:二乙醚易挥发，易燃。远离明火或点火源。 注意:对于方案中的所有洗涤步骤，可以使用另一种溶剂:1）不与被洗涤物质反应，2）不溶解被洗涤物质，3）容易蒸发。 </li></ol></li><li>在最后的洗涤步骤之后，用一个密封Schlenk管润滑塞子并用真空干燥洗涤的N-烷基苯并咪唑产物。干燥后，使用一些纸巾擦拭管口上的油脂，然后将产品转移到一个小瓶中，用于下一个反应。 注意:协议可以在此暂停并在以后恢复。 </li><li>将干净的Schlenk管夹紧并用氩气吹扫，将其内部的空气排出。在管道的侧臂引入气体，并在此过程中保持管子的口部未密封。氩气比空气重，因此从下往上填充管将排出空气。在下一步加入试剂时，继续用氩气吹扫管。 </li><li>将缓慢加入搅拌棒，1mmol N-烷基苯并咪唑，1mmol所选择的烷基卤和4mL无水N ， N-二甲基甲酰胺（DMF）作为溶剂加入到Schlenk管中。一旦添加所有试剂，快速密封管的口用润滑塞子，然后转动旋塞将其侧臂密封，然后关闭氩气。 注意:烷基卤化物是刺激物，可能是有害的。在进行之前，请咨询相关MSDS。 注意: DMF易燃。远离明火或点火源。 </li><li>将密封的Schlenk管放入油浴中，并将反应混合物在80℃下搅拌24小时以使反应完成。 注意:该反应需要在惰性气氛中进行，因此需要谨慎地进行上述涉及氩气的清洗步骤。 </li><li> 24小时后，真空除去混合物中部分DMF溶剂;大约1-2分钟的抽真空应该是足够的。 注意:如果需要， 请从润滑脂混合物中取出所有DMF溶剂，但这不是必需的。 </li><li>开启Schlenk管并加入15 mL乙醚。搅拌哩直到苯并咪唑盐产物沉淀出来。 注意:如果没有乙醚，可以使用石油醚。在进行此建议修改之前，请咨询石油醚的MSDS。 </li><li>沉淀发生后，使用适当的过滤方法除去二乙醚。 注意:我们使用了带有侧臂，内部过滤器和两个开口端的特殊玻璃管，Schlenk管可以连接到该开口端;由于该管上的侧臂和Schlenk管上的侧臂可以附着在真空下，所以该过滤管提供了极大的便利:1）沉淀步骤后的过滤以及洗涤步骤，以及2）洗涤后的干燥脚步。 <ol><li>如果使用类似的东西，将填充的Schlenk管连接到过滤管的一端，另一端将空的Schlenk管连接。然后将空的Schlenk管连接到真空中，并小心地逐渐地翻转设备二乙醚通过过滤器到这个空的Schlenk管。但是，如果不能找到这样的管，请使用其他方法，如用漏斗和滤纸进行过滤。 </li></ol></li><li>用15mL乙醚洗涤盐产物，并使用与步骤1.15中相同的过滤方法除去二乙醚。重复此洗涤步骤几次，使用15 mL乙醚，每次过滤。 </li><li>在最后的洗涤步骤之后，将洗涤后的盐产物干燥（此处，真空干燥过滤管内），然后通过重结晶收集进一步纯化。 注意:协议可以在此暂停并在以后恢复。 </li><li>将盐和乙醇 - 乙醚混合物（12mL:4mL）加入到干净的Schlenk管中。使用热枪加热混合物，直到盐完全溶解。 </li><li>然后，用油脂塞子密封管，并将其夹在几乎水平的位置。离开t他盐在室温下重结晶。 </li><li>一旦盐重结晶，使用一些纸巾擦拭管口的油脂，然后使用漏斗和滤纸过滤混合物以分离盐晶体。 </li><li>洗涤盐晶体，同时仍然在漏斗中的滤纸上，加入15mL二乙醚。重复这个洗涤步骤几次。 </li><li>在最后的洗涤步骤之后，让晶体在滤纸上的空气中干燥。收集纯化的盐进行表征和合成钯NHC复合物。 注意:协议可以在此暂停并在以后恢复。 </li><li>表征盐如前所述18 。 </li></ol> 2.钯NHC配合物的合成和纯化（化合物5-8） <ol><li>将75mL Schlenk管立即夹紧，并加入搅拌棒，1mmol所选择的苯并咪唑盐，1mmol氯化铝，5mmol碳酸钾作为碱和3mL 3-氯吡啶。 注意:氯化钯有毒，可能是刺激性的。 注意:碳酸钾可能是有害的。避免吸入灰尘并远离水分。 注意: 3-氯吡啶极其有害。有毒，有腐蚀性。避免皮肤接触并呼吸其烟雾。 </li><li>用油封塞密封管，并将其放入油浴。将反应混合物在80℃下搅拌16小时，以使钯NHC复合物合成达到完成。 </li><li> 16小时后，让混合物冷却至室温并开启管。向混合物中加入10mL二氯甲烷，以提高下面步骤2.4和2.5中所述的过滤效率;这是可选的，如果需要可以跳过。 注意:二氯甲烷有毒，有刺激性发现疑似致癌物质。避免皮肤接触并呼吸其烟雾。 </li><li>组装以下过滤装置以从反应混合物中除去未反应的氯化钯和苯并咪唑盐:使用不带水龙头的玻璃过滤管。 <ol><li>首先，将四个过滤剂（例如Celite）的铲子添加到管中，以在管的中间的过滤器上方形成过滤剂层。然后，在过滤剂层上方加入四个硅胶粉末。最后，在硅胶层之上挤压一小块棉布，使过滤剂和二氧化硅层固定在过滤器和棉絮之间。 </li></ol></li><li>通过过滤剂和硅胶垫过滤反应混合物如下:将含有反应混合物的Schlenk管连接到玻璃过滤管上，使得Schlenk管与棉絮面对着过滤管的末端。然后，将一个空的Schlenk管连接到另一端过滤管。 <ol><li>将空的Schlenk管连接到真空，小心地逐渐倒置装置，使反应混合物通过（顺序）棉花，二氧化硅，过滤剂和过滤层过滤。未反应的氯化钯和苯并咪唑盐将保留在层中，而含有NHC复合物的滤液将进入空的Schlenk管。 注意:如果将二氯甲烷加入到反应混合物（步骤2.3）中，则可能在过滤管内部产生一些压力，这可能导致液体在反转时从填充的Schlenk管和过滤管之间的连接部分渗出。为了防止这种情况，重要的是在设备倒置之前将空的Schlenk管连接到真空（如上所述），使得在反转时，反应混合物没有足够的时间从上述连接部分渗出。 </li></ol></li><li>分离Schlenk管含有来自上述过滤装置的滤液并用油脂塞子密封。真空除去滤液中的溶剂。 </li><li>一旦除去所有溶剂，开启Schlenk管并加入5mL乙醚洗涤留下的钯NHC复合物产物。轻轻摇动管子进行洗涤。洗完后，用一些纸巾擦拭管子的嘴唇上的油脂，并将乙醚倒入烧杯中。重复此洗涤步骤几次，加入5 mL乙醚，每次滗析。 </li><li>在最后的洗涤步骤之后，用油脂塞子密封Schlenk管，并用真空干燥洗涤的钯NHC复合物产物。干燥后，使用一些纸巾擦拭管口的油脂，然后通过重结晶收集产品进一步净化。 注意:协议可以在此暂停并在以后恢复。 </li><li>对于重结晶，找到一个适用于特定的钯NHC络合物的溶剂（即，该络合物在室温下不容易溶解，但在加热时不易溶解），并按照上述盐相同的步骤（步骤1.18至1.22）。之后，收集纯化的复合物进行表征。 注意:协议可以在此暂停并在以后恢复。 </li><li>表征复杂如前所述18 。 </li></ol>复合物（5-8）在芳基化反应中的催化活性<ol><li>在通风柜内进行空气下的所有催化反应。 </li><li>不经进一步纯化即可使用购买的试剂进行碳 - 碳键形成反应。 </li><li>夹紧25mL Schlenk管，向其中加入搅拌棒，2mmol 2- 正丁基噻吩或2- 正丁基呋喃和1mmol所选择的芳基溴。 注意: 2- 正丁基呋喃和2- 正丁基噻吩均为急性毒性。避免皮肤接触并呼吸其烟雾。 </li><li>然后向管中加入1mmol乙酸钾，0.01mmol所选择的钯NHC配合物和2mL N ， N-二甲基乙酰胺（DMA）。 注意: DMA有毒。避免皮肤接触并呼吸其烟雾。 </li><li>用油封塞密封管，并将其放入油浴。将反应混合物搅拌各种时间并在各种温度下，以找到导致给定反应产物产率最大的时间和温度条件。 注意:反应进程之后可以进行薄层层析（TLC），但是如果只比较不同反应条件对产率的影响（包括用于催化的钯NHC配合物）的影响，则不需要进行反应。在这些情况下，请将反应运行时间少于所需时间完成并改变测试的反应条件。一旦反应进行了所需的时间，通过从反应混合物中除去溶剂来停止反应，如下一步所述。 <ol><li>为了跟随TLC的反应进程，比较反应混合物通过TLC板与反应物的运动;如果混合物仍然产生反应物的斑点，这意味着反应还没有完成。为了在给定的时间后得到反应混合物的样品，在反应仍然运行的同时，开启Schlenk管，并使用毛细管快速获得TLC测试的滴。为了通过TLC板运行混合物和反应物，为特定情况找到合适的溶剂（流动相）。 </li></ol></li><li>一旦反应完成或运行了所需的时间，用真空除去反应混合物中的溶剂。 </li><li>开启Schlenk管，加入己烷 - 乙醚m将混合物（10mL:2mL）加入其中。该溶剂混合物将在下面的步骤3.8和3.9中用于快速柱色谱法的流动相。大力摇动混合物，确保产品溶于流动相，不留在管中。 注意事项:己烷易挥发，易燃。避免吸入烟雾，并远离明火或点火源。 </li><li>如下组装快速色谱柱以净化产品:使用玻璃滴管。首先，将一小块棉花插入滴管中，然后将其推入，直到其紧紧靠在玻璃室开始变薄的地方。然后，将硅胶添加到棉布的顶部，使得三分之二的滴管的厚部分被填充。 </li><li>将硅胶柱直立夹紧并使用玻璃滴管将反应混合物逐渐转移到其中。将混合物通过柱洗脱，并在干净的烧杯或试验中收集含有纯化产物的洗脱液管。 注意:协议可以在此暂停并在以后恢复。 </li><li>将洗脱液转移到可以附着到真空的干净的管子上，并用油脂塞子密封管子。用真空除去洗脱液中的溶剂。 注意:协议可以在此暂停并在以后恢复。 </li><li>一旦除去所有溶剂，开启管并加入1.5mL二氯甲烷。轻轻摇动管子以溶解产物，从而允许其用GC或GC / MS分析。计算使用GC或GC / MS 19，20，21，22，23的产率。 注意:如果二氯甲烷不可用，可以使用氯仿。在进行此建议修改之前，请咨询氯仿的MSDS。 </li></ol> 4.公司的催化活性铃木 - Miyaura交叉偶联反应中的复合物（5-8） <ol><li>根据先前报道的协议18，24进行所有的催化反应。 </li><li>立即将25mL Schlenk管夹紧，向其中加入搅拌棒，1.5mmol苯基硼酸或选择的硼酸衍生物，1mmol所选择的芳基氯和2mmol叔丁醇钠作为碱。 注意事项:苯硼酸及其衍生物是刺激物，有毒。避免皮肤接触。在进行之前，请咨询相关MSDS。 注意:氯化亚芳基是有害的，根据具体化学物质的不同，可能有毒且易燃。在进行之前，请咨询相关MSDS。 注意:叔丁醇钠是易燃固体。在溶液中与水和苛性碱具有高反应性。远离明火或点火源，避免皮肤接触注意:如果没有叔丁醇钠，可以使用氢氧化钾，氢氧化钠，碳酸钾，碳酸钠，乙酸钾，乙酸钠或叔丁醇钾。在进行这些建议的修改之前，请咨询这些基础的MSDS。 </li><li>向管中加入0.01mmol所选择的钯NHC复合物。 </li><li>将DMF-水混合物（2mL:2mL）加入管中。 注意:如果需要，使用较高比例的DMF与水或自己使用DMF。 </li><li>用油封塞密封管，并将其放入油浴。将反应混合物搅拌各种时间并在各种温度下，以找到导致给定反应产物产率最大的时间和温度条件。 注意:反应的进展可以通过TLC进行，但是如果仅比较不同反应条件对产率的影响（包括用于猫的钯NHC复合物分解），然后运行反应完成是没有必要的。在这些情况下，运行反应持续时间小于完成所需的时间，并改变测试的反应条件。一旦反应运行了所需的时间，停下来，继续下一步。为了跟随TLC的反应进程，请参阅步骤3.5.1了解一些细节。 </li><li>一旦反应完成或已经运行所需的时间，就可以将混合物冷却到室温。开启Schlenk管，并向反应混合物中加入己烷 - 乙酸乙酯混合物（5mL:1mL）。重新密封管并将新混合物剧烈摇动数分钟，使合成的产物迁移到己烷 - 乙酸乙酯相。 注意:乙酸乙酯易挥发，易燃，造成严重的眼睛损伤。避免吸入烟雾，并远离明火或点火源。 </li><li>夹住Sch直立管，并使混合物在几分钟的时间内沉淀成两个不同的相。 </li><li>使用玻璃滴管小心地提取顶部有机相，并将其转移到含有1g无水硫酸镁的干净的烧杯中。硫酸镁粉末有助于从提取的有机相中除去任何残留的水。 </li><li>重复步骤4.6至4.8至少一次以最大限度地提取合成产物。 </li><li>按照步骤3.8和3.9，用快速柱色谱纯化产物。提取的有机相中存在的己烷 - 乙酸乙酯混合物将用作该纯化步骤的流动相。在干净的烧杯或试管中收集含有纯化产物的洗脱液。 注意:协议可以在此暂停并在以后恢复。 </li><li>分析产品，并使用GC或GC / MS 19,20计算出产量，21，22，23。 </li></ol>

<ol>
	<li>Akkoc, S., Gok, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+characterization+of+1-phenyl-3-alkylbenzimidazol-2-ylidene+salts+and+their+catalytic+activities+in+the+Heck+and+Suzuki+cross-coupling+reactions.">Synthesis and characterization of 1-phenyl-3-alkylbenzimidazol-2-ylidene salts and their catalytic activities in the Heck and Suzuki cross-coupling reactions.</a> J. Coord. Chem. 66 (8), 1396-1404 (2013).</li><li>Aktas, A., Akkoc, S., Gok, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Palladium+catalyzed+Mizoroki-Heck+and+Suzuki-Miyaura+reactions+using+naphthalenomethyl-substituted+imidazolidin-2-ylidene+ligands+in+aqueous+media.">Palladium catalyzed Mizoroki-Heck and Suzuki-Miyaura reactions using naphthalenomethyl-substituted imidazolidin-2-ylidene ligands in aqueous media.</a> J. Coord. Chem. 66 (16), 2901-2909 (2013).</li><li>Cetinkaya, B., Alici, B., Ozdemir, I., Bruneau, C., Dixneuf, P. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=2-imidazoline+and+1,4,5,6-tetrahydropyrimidine-ruthenium(II)+complexes+and+catalytic+synthesis+of+furan.">2-imidazoline and 1,4,5,6-tetrahydropyrimidine-ruthenium(II) complexes and catalytic synthesis of furan.</a> J. Organomet. Chem. 575 (2), 187-192 (1999).</li><li>Chouthaiwale, P. V., Rawat, V., Sudalai, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Pd-catalyzed+selective+hydrosilylation+of+aryl+ketones+and+aldehydes.">Pd-catalyzed selective hydrosilylation of aryl ketones and aldehydes.</a> Tetrahedron Lett. 53 (2), 148-150 (2012).</li><li>Herrmann, W. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=N-heterocyclic+carbenes:+A+new+concept+in+organometallic+catalysis.">N-heterocyclic carbenes: A new concept in organometallic catalysis.</a> Angew. Chem. Int. Ed. 41 (8), 1290-1309 (2002).</li><li>Jensen, T. R., Schaller, C. P., Hillmyer, M. A., Tolman, W. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Zinc+N-heterocyclic+carbene+complexes+and+their+polymerization+of+D,L-lactide.">Zinc N-heterocyclic carbene complexes and their polymerization of D,L-lactide.</a> J. Organomet. Chem. 690 (24-25), 5881-5891 (2005).</li><li>Lai, Y. B., Lee, C. S., Lin, W. J., Naziruddin, A. R., Hwang, W. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Bis-chelate+N-heterocyclic+tetracarbene+Ru(II)+complexes:+Synthesis,+structure,+and+catalytic+activity+toward+transfer+hydrogenation+of+ketones.">Bis-chelate N-heterocyclic tetracarbene Ru(II) complexes: Synthesis, structure, and catalytic activity toward transfer hydrogenation of ketones.</a> Polyhedron. 53, 243-248 (2013).</li><li>Savka, R. D., Plenio, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+hexahydro-s-indacene+based+NHC+ligand+for+olefin+metathesis+catalysts.">A hexahydro-s-indacene based NHC ligand for olefin metathesis catalysts.</a> J. Organomet. Chem. 710, 68-74 (2012).</li><li>Yigit, M., Yigit, B., Gok, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+novel+palladium(II)+N-heterocyclic+carbene+complexes+and+their+catalytic+activities+in+the+direct+C5+arylation+reactions.">Synthesis of novel palladium(II) N-heterocyclic carbene complexes and their catalytic activities in the direct C5 arylation reactions.</a> Inorg. Chim. Acta. 453, 23-28 (2016).</li><li>Yasar, S., Sahin, C., Arslan, M., Ozdemir, I. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis,+characterization+and+the+Suzuki-Miyaura+coupling+reactions+of+N-heterocyclic+carbene-Pd(II)-pyridine+(PEPPSI)+complexes.">Synthesis, characterization and the Suzuki-Miyaura coupling reactions of N-heterocyclic carbene-Pd(II)-pyridine (PEPPSI) complexes.</a> J. Organomet. Chem. 776, 107-112 (2015).</li><li>Ozdemir, I., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=N-Heterocyclic+carbenes:+Useful+ligands+for+the+palladium-catalysed+direct+C5+arylation+of+heteroaromatics+with+aryl+bromides+or+electron-deficient+aryl+chlorides.">N-Heterocyclic carbenes: Useful ligands for the palladium-catalysed direct C5 arylation of heteroaromatics with aryl bromides or electron-deficient aryl chlorides.</a> Eur. J. Inorg. Chem. 12 (12), 1798-1805 (2010).</li><li>Clavier, H., Nolan, S. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=N-heterocyclic+carbene+and+phosphine+ruthenium+indenylidene+precatalysts:+A+comparative+study+in+Olefin+metathesis.">N-heterocyclic carbene and phosphine ruthenium indenylidene precatalysts: A comparative study in Olefin metathesis.</a> Chem. Eur. J. 13 (28), 8029-8036 (2007).</li><li>Johnson, J. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Catalyzed+reactions+of+acyl+anion+equivalents.">Catalyzed reactions of acyl anion equivalents.</a> Angew. Chem. Int. Ed. 43 (11), 1326-1328 (2004).</li><li>Marion, N., Diez-Gonzalez, S., Nolan, S. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=N-heterocyclic+carbenes+as+organocatalysts.">N-heterocyclic carbenes as organocatalysts.</a> Angew. Chem. Int. Ed. 46 (17), 2988-3000 (2007).</li><li>Perry, M. C., Burgess, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chiral+N-heterocyclic+carbene-transition+metal+complexes+in+asymmetric+catalysis.">Chiral N-heterocyclic carbene-transition metal complexes in asymmetric catalysis.</a> Tetrahedron: Asymmetry. 14 (8), 951-961 (2003).</li><li>Zeitler, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Extending+mechanistic+routes+in+heterazolium+catalysis-promising+concepts+for+versatile+synthetic+methods.">Extending mechanistic routes in heterazolium catalysis-promising concepts for versatile synthetic methods.</a> Angew. Chem. Int. Ed. 44 (46), 7506-7510 (2005).</li><li>Schwarz, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=N-Heterocyclic+carbenes,+part+25+-+Polymer-supported+carbene+complexes+of+palladium:+Well-defined,+air-stable,+recyclable+catalysts+for+the+Heck+reaction.">N-Heterocyclic carbenes, part 25 - Polymer-supported carbene complexes of palladium: Well-defined, air-stable, recyclable catalysts for the Heck reaction.</a> Chem. Eur. J. 6 (10), 1773-1780 (2000).</li><li>Akkoc, S., Gok, Y., Ilhan, I. O., Kayser, V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=N-Methylphthalimide-substituted+benzimidazolium+salts+and+PEPPSI+Pd-NHC+complexes:+synthesis,+characterization+and+catalytic+activity+in+carbon-carbon+bond-forming+reactions.">N-Methylphthalimide-substituted benzimidazolium salts and PEPPSI Pd-NHC complexes: synthesis, characterization and catalytic activity in carbon-carbon bond-forming reactions.</a> Beilstein J. Org. Chem. 12, 81-88 (2016).</li><li>Karaca, E. O., 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=Palladium+complexes+with+tetrahydropyrimidin-2-ylidene+ligands:+Catalytic+activity+for+the+direct+arylation+of+furan,+thiophene,+and+thiazole+derivatives.">Palladium complexes with tetrahydropyrimidin-2-ylidene ligands: Catalytic activity for the direct arylation of furan, thiophene, and thiazole derivatives.</a> Organometallics. 34 (11), 2487-2493 (2015).</li><li>Ozdemir, I., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=N-Heterocyclic+carbene-palladium+catalysts+for+the+direct+arylation+of+pyrrole+derivatives+with+aryl+chlorides.">N-Heterocyclic carbene-palladium catalysts for the direct arylation of pyrrole derivatives with aryl chlorides.</a> Beilstein J. Org. Chem. 9, 303-312 (2013).</li><li>Senocak, A., 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=Synthesis,+crystal+structures,+magnetic+properties+and+Suzuki+and+Heck+coupling+catalytic+activities+of+new+coordination+polymers+containing+tetracyanopalladate(II)+anions.">Synthesis, crystal structures, magnetic properties and Suzuki and Heck coupling catalytic activities of new coordination polymers containing tetracyanopalladate(II) anions.</a> Polyhedron. 49 (1), 50-60 (2013).</li><li>Akkoc, S., Gok, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Dichlorido(3-chloropyridine-N)+1,3-dialkylbenzimidazol-2-ylidene+palladium(II)+complexes:+Synthesis,+characterization+and+catalytic+activity+in+the+arylation+reaction.">Dichlorido(3-chloropyridine-N) 1,3-dialkylbenzimidazol-2-ylidene palladium(II) complexes: Synthesis, characterization and catalytic activity in the arylation reaction.</a> Inorg. Chim. Acta. 429, 34-38 (2015).</li><li>Akkoc, S., Gok, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Catalytic+activities+in+direct+arylation+of+novel+palladium+N-heterocyclic+carbene+complexes.">Catalytic activities in direct arylation of novel palladium N-heterocyclic carbene complexes.</a> Appl. Organomet. Chem. 28 (12), 854-860 (2014).</li><li>Akkoc, S., Gok, Y., Ilhan, I. O., Kayser, V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In+situ+Generation+of+Efficient+Palladium+N-heterocyclic+Carbene+Catalysts+Using+Benzimidazolium+Salts+for+the+Suzuki-Miyaura+Cross-coupling+Reaction.">In situ Generation of Efficient Palladium N-heterocyclic Carbene Catalysts Using Benzimidazolium Salts for the Suzuki-Miyaura Cross-coupling Reaction.</a> Curr. Org. Synth. 13 (5), 761-766 (2016).</li></ol>

作者没有什么可以披露的。

合成和纯化四种苯并咪唑鎓盐，随后他们的钯NHC络合物的方案被故意地提供给最大的细节，以帮助年轻的科学家或那些新的现场掌握他们。考虑到同样的目标，还详细介绍了在芳基化和铃木 - 宫古反应中测试四种络合物的催化活性的方案。此外，我们试图将方案呈现为尽可能一般的形式，以允许其他人容易地适应它们用于许多其它/新的钯NHC复合物的催化活性的合成，纯化和测试。 <p class="jove_c...

N-杂环碳烯（NHC）引起了极大的关注，尤其是其催化各种重要反应的能力，如复分解，呋喃的生成，聚合，氢化硅烷化，氢化，芳基化，铃木 - 宫崎交联和Mizoroki-Heck交联1，2，3，4，5，6，7，8，9，10，11。 NHC可与金属结合;这种金属- NHC络合物作为辅助配体的过渡金属催化的反应被广泛使用和有机催化剂12，13，14， </SUP&gt; 15，16。通常，由于金属 - 碳配位键17的高解离能，其对空气，水分和热量非常稳定。 这里，四个苯并咪唑盐（化合物1 - 4）先前示出的合成和纯化的协议及其钯NHC络合物（化合物5 -分别为8，）是详细18。先前使用各种技术来表征盐和络合物18 。由于用于芳基化和Suzuki-Miyaura交叉偶联反应9，10，11的催化相似的化合物，用于测试复合物的催化活性在芳基化和铃木-宫浦反应的类型，它们在还详细。重要的是，用于合成，纯化和测试复合物的催化活性的方案一般足够容易地适应新的钯NHC络合物。

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>1-chloro-4-nitrobenzene</td>
			<td>Sigma-Aldrich (Interlab A.S., USA)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>2,5-dimethoxyphenylboronic acid</td>
			<td>Sigma-Aldrich (Interlab A.S., USA)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>2-n-butylfuran</td>
			<td>Sigma-Aldrich (Interlab A.S., USA)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>2-n-butylthiophene</td>
			<td>Sigma-Aldrich (Interlab A.S., USA)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>3-chloropyridine</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>4-bromoacetophenone</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>4-bromoanisole</td>
			<td>Sigma-Aldrich (Interlab A.S., USA)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>4-chlorotoluene</td>
			<td>Sigma-Aldrich (Interlab A.S., USA)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>4-methoxy-1-chlorobenzene</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>4-tert-butylphenylboronic acid</td>
			<td>Sigma-Aldrich (Interlab A.S., USA)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Benzimidazole</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Bromobenzene</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Celite</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Dichloromethane</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Diethyl ether</td>
			<td>Sigma-Aldrich (Interlab A.S., USA)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Ethyl acetate</td>
			<td>Sigma-Aldrich (Interlab A.S., USA)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Ethyl alcohol</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Hexane</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Magnesium sulfate</td>
			<td>Scharlau (Barcelona, Spain)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>N,N-dimethylacetamide</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>N,N-dimethylformamide</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Palladium chloride</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Phenylboronic acid</td>
			<td>Sigma-Aldrich (Interlab A.S., USA)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Potassium acetate</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Potassium carbonate</td>
			<td>Scharlau (Barcelona, Spain)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Potassium hydroxide</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Silica gel</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium tert-butoxide</td>
			<td>Merck (Darmstadt, Germany)</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Thianaphthene-2-boronic acid</td>
			<td>Sigma-Aldrich (Interlab A.S., USA)</td>
			<td></td>
			<td></td>
		</tr>
	</tbody>
</table>

palladium n-heterocyclic carbene complexes: synthesis from benzimidazolium salts and catalytic activity in carbon-carbon bond-forming reactions

给出了用于合成和随后从苯并咪唑鎓盐中纯化四种钯N-杂环卡宾络合物的详细和一般化方案。还提供了详细的和一般的方案用于测试这种络合物在芳基化和铃木 - Miyaura交叉偶联反应中的催化活性。显示了四种配合物在芳基化和铃木 - 宫崎型反应中的催化活性的代表性结果。对于所研究的每个反应，四种配合物中的至少一种成功地催化了反应，使它们成为催化许多碳 - 碳键形成反应的有希望的候选物。所提出的方案一般足以适应于新的钯N-杂环卡宾络合物的合成，纯化和催化活性测试。

苯并咪唑的盐（1 - 4）（ 图1）在无水DMF使用N- -alkylbenzimidazoles和各种烷基卤化物，然后纯化和表征合成为前18，24日报道。它们是白色或奶油色固体，产率在62％至97％之间。钯络合物NHC（5 - 8）（ 图2）然后，从盐，纯化的合成...

Watch this Scientific Journal Video about Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions at JoVE.com

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

给出了用于合成和随后从苯并咪唑鎓盐中纯化四种钯N-杂环卡宾络合物的详细和一般化方案。在芳基化和Suzuki-Miyaura反应中测试复合物的催化活性。对于所研究的每个反应，四种配合物中的至少一种成功地催化了反应。

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 ...

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

Chemical Bonding: Basic Concepts

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9.6K 次观看.  The University of Sydney. 给出了用于合成和随后从苯并咪唑鎓盐中纯化四种钯N-杂环卡宾络合物的详细和一般化方案。在芳基化和Suzuki-Miyaura反应中测试复合物的催化活性。对于所研究的每个反应，四种配合物中的至少一种成功地催化了反应。 

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

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

Anticancer Metal Complexes: Synthesis and Cytotoxicity Evaluation by the MTT Assay

Titanium (IV) and vanadium (V) complexes are highly potent anticancer agents. A challenge in their synthesis refers to their hydrolytic instability; therefore their preparation should be conducted under an inert atmosphere. Evaluation of the anticancer activity of these complexes can be achieved by the MTT assay.
The MTT assay is a colorimetric viability assay based on enzymatic reduction of the MTT molecule to formazan when it is exposed to viable cells. The outcome of the reduction is a color change of the MTT molecule. Absorbance measurements relative to a control determine the percentage of remaining viable cancer cells following their treatment with varying concentrations of a tested compound, which is translated to the compound anticancer activity and its IC50 values. The MTT assay is widely common in cytotoxicity studies due to its accuracy, rapidity, and relative simplicity.
Herein we present a detailed protocol for the synthesis of air sensitive metal based drugs and cell viability measurements, including preparation of the cell plates, incubation of the compounds with the cells, viability measurements using the MTT assay, and determination of IC50 values.

A method for synthesis of air-sensitive titanium and vanadium anticancer agents is described, along with the evaluation of their cytotoxic activity towards human cancer cell line by the MTT Assay.

抗癌金属配合物的合成与细胞毒性评价MTT法

Titanium (IV) and vanadium (V) complexes are highly potent anticancer agents. A challenge in their synthesis refers to their hydrolytic instability; ...

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

Unsymmetrical 1,2-diols are hardly accessible by reductive pinacol coupling processes. A successful execution of such a transformation is bound to a clear recognition and strict differentiation of two similar carbonyl compounds (aldehydes &#8594; secondary 1,2-diols or ketones &#8594; tertiary 1,2-diols). This fine-tuning is still a challenge and an unsolved problem for an organic chemist. There exist several reports on successful execution of this transformation but they cannot be generalized. Herein we describe a catalytic direct pinacol coupling process which proceeds via a retropinacol/cross-pinacol coupling sequence. Thus, unsymmetrical substituted 1,2-diols can be accessed with almost quantitative yields by means of an&#160;operationally simple performance under very mild conditions. Artificial techniques, such as syringe-pump techniques or delayed additions of reactants are not necessary. The procedure we describe provides a very rapid access to cross-pinacol products (1,2-diols, vicinal diols). A further extension of this new process, e.g. an enantioselective performance could provide a very useful tool for the synthesis of unsymmetrical chiral 1,2-diols.

A novel account for the synthesis of unsymmetrical 1,2-diols based on a retropinacol/cross-pinacol coupling mechanism is described. Due to the catalytic execution of this reaction a considerable improvement compared to conventional cross-pinacol couplings is achieved.

Retropinacol /跨频哪醇偶联反应 - 催化访问1,2  - 非对称二醇

Unsymmetrical 1,2-diols are hardly accessible by reductive pinacol coupling processes. A successful execution of such a transformation is bound to a clear ...

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 ...

Synthesis and Catalytic Performance of Gold Intercalated in the Walls of Mesoporous Silica

As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties of the materials were investigated. We used a one pot sol-gel approach to intercalate gold nano particles in the walls of mesoporous silica. To start with the synthesis, P123 was used as template to form micelles. Then TESPTS was used as a surface modification agent to intercalate gold nano particles. Following this process, TEOS was added in as a silica source which underwent a polymerization process in acid environment. After hydrothermal processing and calcination, the final product was acquired. Several techniques were utilized to characterize the porosity, morphology and structure of the gold intercalated mesoporous silica. The results showed a stable structure of mesoporous silica after gold intercalation. Through the oxidation of benzyl alcohol as a benchmark reaction, the GMS materials showed high selectivity and recyclability.

Here, we present a protocol with a sol-gel process to synthesize gold intercalated in the walls of mesoporous materials (GMS), which is confirmed to possess a mesoporous matrix with gold intercalated in the walls imparting great stability and recyclability.

合成和金插在介孔二氧化硅的墙壁催化性能

As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties ...

Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts

Ynones are a valuable functional group and building block in organic synthesis. Ynones serve as a precursor to many important organic functional groups and scaffolds. Traditional methods for the preparation of ynones are associated with drawbacks including harsh conditions, multiple purification steps, and the presence of unwanted byproducts. An alternative method for the straightforward preparation of ynones from acyl chlorides and potassium alkynyltrifluoroborate salts is described herein. The adoption of organotrifluoroborate salts as an alternative to organometallic reagents for the formation of new carbon-carbon bonds has a number of advantages. Potassium organotrifluoroborate salts are shelf stable, have good functional group tolerance, low toxicity, and a wide variety are straightforward to prepare. The title reaction proceeds rapidly at ambient temperature in the presence of a Lewis acid without the exclusion of air and moisture. Fair to excellent yields may be obtained via reaction of various aryl and alkyl acid chlorides with alkynyltrifluoroborate salts in the presence of boron trichloride.

The goal of this manuscript is to demonstrate a straightforward method for the preparation of ynones from acyl chloride and potassium alkynyltrifluoroborate salt starting materials. The one-pot reaction proceeds rapidly in the presence of boron trichloride without exclusion of air and moisture.

Ynones从酰氯和钾Alkynyltrifluoroborate盐无金属合成

Ynones are a valuable functional group and building block in organic synthesis. Ynones serve as a precursor to many important organic functional groups ...

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

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the hydroxylmethylene phosphine precursor with ammonia in methanol under a nitrogen atmosphere. The N-triphosPh ligand precipitates from the solution after approximately 1 hr of reflux and can be isolated analytically pure via simple cannula filtration procedure under nitrogen. Reaction of the N-triphosPh ligand with [Ru3(CO)12] under reflux affords a deep red solution that show evolution of CO gas on ligand complexation. Orange crystals of the complex [Ru(CO)2{N(CH2PPh2)3}-&#954;3P] (2) were isolated on cooling to RT. The 31P{1H} NMR spectrum showed a characteristic single peak at lower frequency compared to the free ligand. Reaction of a toluene solution of complex 2 with oxygen resulted in the instantaneous precipitation of the carbonate complex [Ru(CO3)(CO){N(CH2PPh2)3}-&#954;3P] (3) as an air stable orange solid. Subsequent hydrogenation of 3 under 15 bar of hydrogen in a high-pressure reactor gave the dihydride complex [RuH2(CO){N(CH2PPh2)3}-&#954;3P] (4), which was fully characterized by X-ray crystallography and NMR spectroscopy. Complexes 3 and 4 are potentially useful catalyst precursors for a range of hydrogenation reactions, including biomass-derived products such as levulinic acid (LA). Complex 4 was found to cleanly react with LA in the presence of the proton source additive NH4PF6 to give [Ru(CO){N(CH2PPh2)3}-&#954;3P{CH3CO(CH2)2CO2H}-&#954;2O](PF6) (6).

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

Ruthenium phosphine complexes are widely used for homogeneous catalytic reactions such as hydrogenations. The synthesis of a series of novel tridentate ruthenium complexes bearing the N-triphos ligand N(CH2PPh2)3 is reported. Additionally, the stoichiometric reaction of a dihydride Ru&#8211;N-triphos complex with levulinic acid is described.

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 ...

Laboratory Production of Biofuels and Biochemicals from a Rapeseed Oil through Catalytic Cracking Conversion

The work is based on a reported study which investigates the processability of canola oil (bio-feed) in the presence of bitumen-derived heavy gas oil (HGO) for production of transportation fuels through a fluid catalytic cracking (FCC) route. Cracking experiments are performed with a fully automated reaction unit at a fixed weight hourly space velocity (WHSV) of 8 hr-1, 490-530 &#176;C, and catalyst/oil ratios of 4-12 g/g. When a feed is in contact with catalyst in the fluid-bed reactor, cracking takes place generating gaseous, liquid, and solid products. The vapor produced is condensed and collected in a liquid receiver at -15 &#176;C. The non-condensable effluent is first directed to a vessel and is sent, after homogenization, to an on-line gas chromatograph (GC) for refinery gas analysis. The coke deposited on the catalyst is determined in situ by burning the spent catalyst in air at high temperatures. Levels of CO2 are measured quantitatively via an infrared (IR) cell, and are converted to coke yield. Liquid samples in the receivers are analyzed by GC for simulated distillation to determine the amounts in different boiling ranges, i.e., IBP-221 &#176;C (gasoline), 221-343 &#176;C (light cycle oil), and 343 &#176;C+ (heavy cycle oil). Cracking of a feed containing canola oil generates water, which appears at the bottom of a liquid receiver and on its inner wall. Recovery of water on the wall is achieved through washing with methanol followed by Karl Fischer titration for water content. Basic results reported include conversion (the portion of the feed converted to gas and liquid product with a boiling point below 221 &#176;C, coke, and water, if present) and yields of dry gas (H2-C2's, CO, and CO2), liquefied petroleum gas (C3-C4), gasoline, light cycle oil, heavy cycle oil, coke, and water, if present.

This paper presents an experimental method to produce biofuels and biochemicals from canola oil mixed with a fossil-based feed in the presence of a catalyst at mild temperatures. Gaseous, liquid, and solid products from a reaction unit are quantified and characterized. Conversion and individual product yields are calculated and reported.

通过催化裂化转换从菜籽油生物燃料和生物化学实验室生产

The work is based on a reported study which investigates the processability of canola oil (bio-feed) in the presence of bitumen-derived heavy gas oil ...

Enzymatic Cascade Reactions for the Synthesis of Chiral Amino Alcohols from L-lysine

Amino alcohols are versatile compounds with a wide range of applications. For instance, they have been used as chiral scaffolds in organic synthesis. Their synthesis by conventional organic chemistry often requires tedious multi-step synthesis processes, with difficult control of the stereochemical outcome. We present a protocol to enzymatically synthetize amino alcohols starting from the readily available L-lysine in 48 h. This protocol combines two chemical reactions that are very difficult to conduct by conventional organic synthesis. In the first step, the regio- and diastereoselective oxidation of an unactivated C-H bond of the lysine side-chain is catalyzed by a dioxygenase; a second regio- and diastereoselective oxidation catalyzed by a regiodivergent dioxygenase can lead to the formation of the 1,2-diols. In the last step, the carboxylic group of the alpha amino acid is cleaved by a pyridoxal-phosphate (PLP) decarboxylase (DC). This decarboxylative step only affects the alpha carbon of the amino acid, retaining the hydroxy-substituted stereogenic center in a beta/gamma position. The resulting amino alcohols are therefore optically enriched. The protocol was successfully applied to the semipreparative-scale synthesis of four amino alcohols. Monitoring of the reactions was conducted by high performance liquid chromatography (HPLC) after derivatization by 1-fluoro-2,4-dinitrobenzene. Straightforward purification by solid-phase extraction (SPE) afforded the amino alcohols with excellent yields (93% to &#62;95%).

Chiral amino alcohols are versatile molecules for use as scaffolds in organic synthesis. Starting from L-lysine, we synthesize amino alcohols by an enzymatic cascade reaction combining diastereoselective C-H oxidation catalyzed by dioxygenase followed by cleavage of the carboxylic acid moiety of the corresponding hydroxyl amino acid by a decarboxylase.

酶联反应合成 l-赖氨酸手性氨基醇的研究

Amino alcohols are versatile compounds with a wide range of applications. For instance, they have been used as chiral scaffolds in organic synthesis. ...

Chemical Precipitation Method for the Synthesis of Nb2O5 Modified Bulk Nickel Catalysts with High Specific Surface Area

We demonstrate a method for the synthesis of NixNb1-xO catalysts with sponge-like and fold-like nanostructures. By varying the Nb:Ni ratio, a series of NixNb1-xO nanoparticles with different atomic compositions (x = 0.03, 0.08, 0.15, and 0.20) have been prepared by chemical precipitation. These NixNb1-xO catalysts are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The study revealed the sponge-like and fold-like appearance of Ni0.97Nb0.03O and Ni0.92Nb0.08O on the NiO surface, and the larger surface area of these NixNb1-xO catalysts, compared with the bulk NiO. Maximum surface area of 173 m2/g can be obtained for Ni0.92Nb0.08O catalysts. In addition, the catalytic hydroconversion of lignin-derived compounds using the synthesized Ni0.92Nb0.08O catalysts have been investigated.

Chemical Precipitation Method for the Synthesis of Nb2O5 Modified Bulk Nickel Catalysts with High Specific Surface Area

A protocol for the synthesis of sponge-like and fold-like Ni1-xNbxO nanoparticles by chemical precipitation is presented.

化学沉淀法合成铌2O5改性高比表面积镍催化剂

We demonstrate a method for the synthesis of NixNb1-xO catalysts with sponge-like and fold-like nanostructures. By varying the Nb:Ni ratio, a series of ...