Name: [(dpephos)(bcp)cu]pf6: a general and broadly applicable copper-based photoredox catalyst
Uploaded: 2019-05-21T14:45:00
Description: Watch this Scientific Journal Video about [DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst at JoVE.com

这项工作得到了布鲁塞尔自由大学 (ULB)、Wallone-bruxleles 联合会 (ARC 合作者 2014-2019)、Innoviris (photocop 项目) 和咖啡和工业和工程部行动 CM1202 的支持。H. b. 承认 "勒彻切之山" 为研究生奖学金。C. t. 承认《科学研究基金会》 (FNRS) 的研究金。

1. [(Dpepphos) (bcp) Cu] PF6的合成
<ol><li>加入 3.73 g (10.00 mmol) 四乙腈铜 (I) 六氟磷酸铜和5.39 克 (10.00 mmol) 的 Dpepphos 到一个2升圆形底瓶配备了磁搅拌杆。</li>
	<li>将圆底瓶与连接到真空线和氩线的三个颈部真空适配器配合使用。</li>
	<li>在真空下疏散烧瓶, 并用氩回填三次。用橡胶隔膜代替三个颈部真空适配器。 注: 反应可以在空气中进行, 效率略有下降 (详见讨论部分)。</li>
	<li>加入800毫升?...

<ol>
	<li>Chatgilialoglu, C., Studer, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Encyclopedia of Radicals in Chemistry, Biology and Materials. , (2012).</li><li>Narayanam, J. M. R., Stephenson, C. R. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Visible+light+photoredox+catalysis:+applications+in+organic+synthesis.">Visible light photoredox catalysis: applications in organic synthesis.</a> Chemical Society Reviews. 40, 102-113 (2011).</li><li>Prier, C. K., Rankic, D. A., MacMillan, D. W. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Visible+Light+Photoredox+Catalysis+with+Transition+Metal+Complexes:+Applications+in+Organic+Synthesis.">Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis.</a> Chemical Reviews. 113 (7), 5322-5363 (2013).</li><li>Romero, N. A., Nicewicz, D. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Organic+Photoredox+Catalysis.">Organic Photoredox Catalysis.</a> Chemical Reviews. 116 (17), 10075 (2016).</li><li>Paria, S., Reiser, O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Copper+in+Photocatalysis.">Copper in Photocatalysis.</a> ChemCatChem. 6 (9), 2477-2483 (2014).</li><li>Reiser, O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Shining+Light+on+Copper:+Unique+Opportunities+for+Visible-Light-Catalyzed+Atom+Transfer+Radical+Addition+Reactions+and+Related+Processes.">Shining Light on Copper: Unique Opportunities for Visible-Light-Catalyzed Atom Transfer Radical Addition Reactions and Related Processes.</a> Accounts of Chemical Research. 49 (9), 1990-1996 (2016).</li><li>Boyer, C., 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=Copper-Mediated+Living+Radical+Polymerization+(Atom+Transfer+Radical+Polymerization+and+Copper(0)+Mediated+Polymerization):+From+Fundamentals+to+Bioapplications.">Copper-Mediated Living Radical Polymerization (Atom Transfer Radical Polymerization and Copper(0) Mediated Polymerization): From Fundamentals to Bioapplications.</a> Chemical Reviews. 116 (4), 1803-1949 (2016).</li><li>Paria, S., Reiser, O., Stephenson, C. R. J., Yoon, T. P., MacMillan, D. W. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Visible+Light+and+Copper+Complexes:+A+Promising+Match+in+Photoredox+Catalysis.">Visible Light and Copper Complexes: A Promising Match in Photoredox Catalysis.</a> Visible Light Photocatalysis in Organic Chemistry. , 233-252 (2018).</li><li>Grutsch, P. A., Kutal, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photobehavior+of+copper(I)+compounds.+Role+of+copper(I)-phosphine+compounds+in+the+photosensitized+isomerization+of+norbornadiene.">Photobehavior of copper(I) compounds. Role of copper(I)-phosphine compounds in the photosensitized isomerization of norbornadiene.</a> Journal of the American Chemical Society. 101 (15), 4228-4233 (1979).</li><li>Mitani, M., Kato, I., Koyama, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photoaddition+of+alkyl+halides+to+olefins+catalyzed+by+copper(I)+complexes.">Photoaddition of alkyl halides to olefins catalyzed by copper(I) complexes.</a> Journal of the American Chemical Society. 105 (22), 6719-6721 (1983).</li><li>Kern, J. -. M., Sauvage, J. -. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photoassisted+C-C+coupling+via+electron+transfer+to+benzylic+halides+by+a+bis(di-imine)+copper(I)+complex.">Photoassisted C-C coupling via electron transfer to benzylic halides by a bis(di-imine) copper(I) complex.</a> Journal of the Chemical Society, Chemical Communications. , 546-548 (1987).</li><li>Creutz, S. E., Lotito, K. J., Fu, G. C., Peters, J. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photoinduced+Ullmann+C-N+coupling:+demonstrating+the+viability+of+a+radical+pathway.">Photoinduced Ullmann C-N coupling: demonstrating the viability of a radical pathway.</a> Science. 338 (6107), 647-651 (2012).</li><li>Kainz, Q. M., Matier, C. D., Bartoszewicz, A., Zultanski, S. L., Peters, J. C., Fu, G. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Asymmetric+copper-catalyzed+C-N+cross-couplings+induced+by+visible+light.">Asymmetric copper-catalyzed C-N cross-couplings induced by visible light.</a> Science. 351 (6274), 681-684 (2016).</li><li>Matier, C. D., Schwaben, J., Peters, J. C., Fu, G. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Copper-Catalyzed+Alkylation+of+Aliphatic+Amines+Induced+by+Visible+Light.">Copper-Catalyzed Alkylation of Aliphatic Amines Induced by Visible Light.</a> Journal of the American Chemical Society. 139 (49), 17707-17710 (2017).</li><li>He, J., Chen, C., Fu, G. C., Peters, J. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Visible-Light-Induced,+Copper-Catalyzed+Three-Component+Coupling+of+Alkyl+Halides,+Olefins+and+Trifluoromethylthiolate+to+Generate+Trifluoromethyl+Thioethers.">Visible-Light-Induced, Copper-Catalyzed Three-Component Coupling of Alkyl Halides, Olefins and Trifluoromethylthiolate to Generate Trifluoromethyl Thioethers.</a> ACS Catalysis. 8 (12), 11741-11748 (2018).</li><li>Pirtsch, M., Paria, S., Matsuno, T., Isobe, H., Reiser, O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=[Cu(dap)2Cl]+As+an+Efficient+Visible-Light-Driven+Photoredox+Catalyst+in+Carbon-Carbon+Bond-Forming+Reactions.">[Cu(dap)2Cl] As an Efficient Visible-Light-Driven Photoredox Catalyst in Carbon-Carbon Bond-Forming Reactions.</a> Chemistry - A European Journal. 18 (24), 7336-7340 (2012).</li><li>Paria, S., Pirtsch, M., Kais, V., Reiser, O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Visible-Light-Induced+Intermolecular+Atom-Transfer+Radical+Addition+of+Benzyl+Halides+to+Olefins:+Facile+Synthesis+of+Tetrahydroquinolines.">Visible-Light-Induced Intermolecular Atom-Transfer Radical Addition of Benzyl Halides to Olefins: Facile Synthesis of Tetrahydroquinolines.</a> Synthesis. 45 (19), 2689-2698 (2013).</li><li>Knorn, M., Rawner, T., Czerwieniec, R., Reiser, O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=[Copper(phenanthroline(bisisonitrile)]+-Complexes+for+the+Visible-Light-Mediated+Atom+Transfer+Radical+Addition+and+Allylation+Reactions.">[Copper(phenanthroline(bisisonitrile)]+-Complexes for the Visible-Light-Mediated Atom Transfer Radical Addition and Allylation Reactions.</a> ACS Catalysis. 5 (9), 5186-5193 (2015).</li><li>Bagal, D. B., Kachkovskyi, G., Knorn, M., Rawner, T., Bhanage, B. M., Reiser, O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Trifluoromethylchlorosulfonylation+of+Alkenes:+Evidence+for+an+Inner-Sphere+Mechanism+by+a+Copper+Phenanthroline+Photoredox+Catalyst.">Trifluoromethylchlorosulfonylation of Alkenes: Evidence for an Inner-Sphere Mechanism by a Copper Phenanthroline Photoredox Catalyst.</a> Angewandte Chemie International Edition. 54 (24), 6999-7002 (2015).</li><li>Hossain, 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=Visible-Light-Accelerated+Copper(II)-Catalyzed+Regio-+and+Chemoselective+Oxo-Azidation+of+Vinyl+Arenes.">Visible-Light-Accelerated Copper(II)-Catalyzed Regio- and Chemoselective Oxo-Azidation of Vinyl Arenes.</a> Angewandte Chemie International Edition. 57 (27), 8288-8292 (2018).</li><li>Hernandez-Perez, A. C., Vlassova, A., Collins, S. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Toward+a+Visible+Light+Mediated+Photocyclization:+Cu-Based+Sensitizers+for+the+Synthesis+of+[5]Helicene.">Toward a Visible Light Mediated Photocyclization: Cu-Based Sensitizers for the Synthesis of [5]Helicene.</a> Organic Letters. 14 (12), 2988-2991 (2012).</li><li>Baralle, A., Fensterbank, L., Goddard, J. -. P., Ollivier, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Aryl+Radical+Formation+by+Copper(I)+Photocatalyzed+Reduction+of+Diaryliodonium+Salts:+NMR+Evidence+for+a+CuII/CuI+Mechanism.">Aryl Radical Formation by Copper(I) Photocatalyzed Reduction of Diaryliodonium Salts: NMR Evidence for a CuII/CuI Mechanism.</a> Chemistry - A European Journal. 19 (23), 10809-10813 (2013).</li><li>Hernandez-Perez, A. C., Collins, S. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Visible-Light-Mediated+Synthesis+of+Carbazole.">A Visible-Light-Mediated Synthesis of Carbazole.</a> Angewandte Chemie International Edition. 52 (48), 12696-12700 (2013).</li><li>Tang, X. -. J., Doldier, W. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Efficient+Cu-catalyzed+Atom+Transfer+Radical+Addition+Reactions+of+Fluoroalkylsulfonyl+Chlorides+with+Electron-Deficient+Alkenes+Induced+by+Visible+Light.">Efficient Cu-catalyzed Atom Transfer Radical Addition Reactions of Fluoroalkylsulfonyl Chlorides with Electron-Deficient Alkenes Induced by Visible Light.</a> Angewandte Chemie International Edition. 54 (14), 4246-4249 (2015).</li><li>Fumagalli, G., Rabet, P. T. G., Boyd, S., Greaney, M. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Three-Component+Azidation+of+Styrene-Type+Double+Bonds:+Light-Switchable+Behavior+of+a+Copper+Photoredox+Catalyst.">Three-Component Azidation of Styrene-Type Double Bonds: Light-Switchable Behavior of a Copper Photoredox Catalyst.</a> Angewandte Chemie International Edition. 54 (39), 11481-11484 (2015).</li><li>Demmer, C. S., Benoit, E., Evano, G. <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+Allenamides+by+Copper-Catalyzed+Coupling+of+Propargylic+Bromides+and+Nitrogen+Nucleophiles.">Synthesis of Allenamides by Copper-Catalyzed Coupling of Propargylic Bromides and Nitrogen Nucleophiles.</a> Organic Letters. 18 (6), 1438-1441 (2016).</li><li>Theunissen, C., Wang, J., Evano, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Copper-catalyzed+direct+alkylation+of+heteroarenes.">Copper-catalyzed direct alkylation of heteroarenes.</a> Chemical Science. 8, 3465-3470 (2017).</li><li>Michelet, B., Deldaele, C., Kajouj, S., Moucheron, C., Evano, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+General+Copper+Catalyst+for+Photoredox+Transformations+of+Organic+Halides.">A General Copper Catalyst for Photoredox Transformations of Organic Halides.</a> Organic Letters. 19 (13), 3576-3579 (2017).</li><li>Baguia, H., Deldaele, C., Romero, E., Michelet, B., Evano, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Copper-Catalyzed+Photoinduced+Radical+Domino+Cyclization+of+Ynamides+and+Cyanamides:+A+Unified+Entry+to+Rosettacin,+Luotonin+A,+and+Deoxyvasicinone.">Copper-Catalyzed Photoinduced Radical Domino Cyclization of Ynamides and Cyanamides: A Unified Entry to Rosettacin, Luotonin A, and Deoxyvasicinone.</a> Synthesis. 50 (15), 3022-3030 (2018).</li><li>Deldaele, C., Michelet, B., Baguia, H., Kajouj, S., Romero, E., Moucheron, C., Evano, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+General+Copper-based+Photoredox+Catalyst+for+Organic+Synthesis:+Scope+Application+in+Natural+Product+Synthesis+and+Mechanistic+Insights.">A General Copper-based Photoredox Catalyst for Organic Synthesis: Scope Application in Natural Product Synthesis and Mechanistic Insights.</a> CHIMIA. 72 (9), 621-629 (2018).</li><li>Luo, S. -. P., 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=Photocatalytic+Water+Reduction+with+Copper-Based+Photosensitizers:+A+Noble-Metal-Free+System.">Photocatalytic Water Reduction with Copper-Based Photosensitizers: A Noble-Metal-Free System.</a> Angewandte Chemie International Edition. 52 (1), 419-423 (2013).</li><li>Gryko, D. T., Vakuliuk, O., Gryko, D., Koszarna, B. <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+2-Arylation+of+Pyrroles.">Palladium-Catalyzed 2-Arylation of Pyrroles.</a> The Journal of Organic Chemistry. 74 (24), 9517-9520 (2009).</li><li>Servais, A., Azzouz, M., Lopes, D., Courilon, C., Malacria, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Radical+Cyclization+of+N-Acylcyanamides:+Total+Synthesis+of+Luotonin+A.">Radical Cyclization of N-Acylcyanamides: Total Synthesis of Luotonin A.</a> Angewandte Chemie International Edition. 46 (4), 576-579 (2007).</li><li>Cambi&#233;, D., Bottecchia, C., Straathof, N. J. W., Hessel, V., No&#235;l, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Applications+of+Continuous-Flow+Photochemistry+in+Organic+Synthesis,+Material+Science,+and+Water+Treatment.">Applications of Continuous-Flow Photochemistry in Organic Synthesis, Material Science, and Water Treatment.</a> Chemical Reviews. 116 (17), 10276-10341 (2016).</li><li>Straathof, N. J. W., No&#235;l, T., Stephenson, C. R. J., Yoon, T. P., MacMillan, D. W. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Accelerating+Visible-Light+Photoredox+Catalysis+in+Continuous-Flow+Reactors.">Accelerating Visible-Light Photoredox Catalysis in Continuous-Flow Reactors.</a> Visible Light Photocatalysis in Organic Chemistry. , 389-413 (2018).</li><li>Marion, F., Courillon, C., Malacria, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Radical+Cyclization+Cascade+Involving+Ynamides:+An+Original+Access+to+Nitrogen-Containing+Heterocycles.">Radical Cyclization Cascade Involving Ynamides: An Original Access to Nitrogen-Containing Heterocycles.</a> Organic Letters. 5 (26), 5095-5097 (2003).</li><li>Han, Y. -. Y., Jiang, H., Wang, R., Yu, S. <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+Tetracyclic+Quinazolinones+Using+a+Visible-Light-Promoted+Radical+Cascade+Approach.">Synthesis of Tetracyclic Quinazolinones Using a Visible-Light-Promoted Radical Cascade Approach.</a> The Journal of Organic Chemistry. 81 (16), 7276-7281 (2016).</li></ol>

[(Dpepphos) (bcp) Cu] PF6的合成 [(DPEPhos) (bcp) cu] PF6的合成通常使用干二氯甲烷 (使用前蒸馏) 和氩下进行, 以确保最高的产量、纯度和良好的重现性。如议定书所述, [(Dpepphos) (bcp) cu] PF6的合成可以用普通的二氯甲烷进行 (99.8%)在空气中, 效率可变。事实上, 虽然在氩下使用普通的二氯甲烷具有同样的效率 (产量为 89%), 但在空气下使用蒸馏二氯甲烷只能提供所需的复合...

在合成化学中, 自由基转化已经被认为是非常有效的途径, 而合成化学往往是基于阳离子、阴离子或环环过程1的转化的补充。虽然对各种转化特别有希望, 但基于激进的化学长期以来一直没有得到充分利用, 主要原因是需要剧毒试剂, 这大大限制了其吸引力。此外, 自由基过程长期以来一直被认为是与区域和立体选择性控制水平低有关的转变, 或导致广泛的二聚和/或聚合问题。
最近制定了替代战略, 以促进自由基物种的产生和更好地控制其反应性。其中, 光合毒素催化已成为最有力的方法之一, 因为它允许使用光响应化合物, 即光氏杆菌催化剂和可见光照射2, 3,方便地生成自由基物种.可见光本身确实能够促进光数催化剂激发状态的种群, 因此, 光数催化剂既能成为一种更强的还原剂, 也能成为其相应的基态。这些增强的氧化还原特性使得单电子转移过程在激发态的温和条件下成为可能, 在基态条件下是不可行的。在过去的十年里, 可见光光合牛催化已成为有机合成中一种有吸引力和强大的技术, 并使许多基于自由基中间体的非常高效和选择性的转化得以发展在可持续、温和和方便用户的条件下产生。
虽然迄今报告的大多数光比多克工艺主要是使用以锂和红宝石为基础的光合酶催化剂, 以及一些有机染料, 如吡咯和丙烯衍生物4, 但对更便宜的替代品的要求仍然很高用于开发工业应用中感兴趣的互补工艺。在这方面, 使用基于铜的光影毒催化剂似乎特别吸引人, 因为它们不仅更便宜, 而且还提供了激活更广泛和/或不同范围的基板的机会, 从而开辟了新的前景。光合催化5,6,7, 8.尽管库塔尔9号、米塔尼10和绍瓦奇11组报道了一些有希望的早期作品, 但光可活动铜质综合体几乎没有用于光毒杆菌催化, 很可能是因为它们与以和为基础的同源物相比, 短命的兴奋状态。最近, 彼得斯和傅做出了显著的贡献,12,13, 14, 15, reiser16,17,18 ,19,20组和其他组21,22,23, 24,25显然已经引起了人们的注意, 铜基光合酶催化剂, 并证明了他们的独特的潜力。
作为我们最近对铜催化自由基工艺的兴趣的一部分26,27, 我们最近报告了一个普遍和广泛适用的铜基光影量催化剂, [(dpephos) (bcp) cu] pf6 (dpephos: bis[(2-苯醚;bcp: 基波林), 它被证明是特别有效的激活有机卤化物在可见光照射下 (图 1a)28,29,30。在可见光照射下, 在作为牺牲还原剂的胺存在的情况下, 大量未活化的芳基和烷基卤化物被催化量 [(Dpepphos) (Bcp) Cu] pf]6 (因此参与) 很容易激活在各种彻底的转变中, 包括几种富含电子 (异种) 的芳烃的还原、环切和直接芳基化。此外, [(Dpepphos) (bcp) Cu] PF6也已被证明成功地促进了动力学剂和氰化物的光诱导的自由基多米诺骨牌化, 提供了一个有效和直接的访问复杂的三、四联和五环氮杂环是各种天然产物的核心结构。这一策略使迷他汀、罗托宁 a 和脱氧血管素的天然产物具有抗癌、抗菌、抗炎和抗抑郁活性, 从而有效地合成了。这些转换如图 1C所示。从机械角度来看, 用 [(Dpepphos) (Bcp) cu] PF6光诱导活化是通过一个罕见的 Cu(I)/Cu(I)*/Cu(0) 催化循环进行的, 这一点已得到广泛的机械和光物理研究的证实。特别是, 激发的基态 [(Dpepphos) (bcp) Cu] pf 6 [cu (i)] 后, 由可见光照射导致形成相应的激发复合体 [(dpepphos) (bcp) cu] pf6* [cu (i) *], 然后减少由牺牲胺产生相应的 [(Dpepphos) (bcp) cu] pf6 [Cu(0)]。这种 Cu(0) 中间体还原到足以减少各种有机卤化物的碳-卤素键, 从而产生相应的自由基, 然后可以参与上述转变, 同时再生启动(图 1 b)。
在下一节中, 我们首先描述了合成光电可的协议 [(Dpepphos) (bcp) Cu] PF6 (其核磁共振和光谱特征在代表性结果部分中介绍)。合成是简单的, 特别方便, 只需要添加1个相当于 Dpepphos 和1个相当于 bcp 的六氯甲烷中的四乙酰基二腈铜 (I) 溶液中的 bcp。然后通过二乙醚的沉淀分离所需的 [(dpepphos) (Bcp) cu] PF 6 , 并且可以很容易地在多克尺度上获得 (图 2 a)。重要的是, 隔离的铜复合体对氧气和水分不是特别敏感, 因此可以方便地处理, 除了远离光线存储之外, 没有其他具体的预防措施。
其次, 我们描述了使用 [(Dpepphos) (Bcp) cu] PF6激活有机卤化物的协议, 重点是两个不同的转变。第一反应是用催化量 [(Dpepphos) (Bcp) cu] PF 6 作为光角上克催化剂, 二环己基异丁胺作为牺牲还原剂和钾, 用 4-碘苯酮腈直接酰化作为在420纳米辐照下的碱基 (图 2B)。第二反应是n-苯甲酰-n-[(2-碘喹啉-3-基) 甲基] 氰氨化的自由基化, 使用相同的催化剂和牺牲还原剂, 其环化直接导致罗托宁 a, 一种天然产品显示有趣的抗癌活动 (图 2c)。为这两个转换提供了详细的协议。

<table border="0" cellpadding="0" cellspacing="0" style="width:572px;" width="573">
	<colgroup>
		<col />
		<col />
		<col />
		<col />
	</colgroup>
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Material</td>
			<td style="width:71px;"></td>
			<td style="width:119px;"></td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Bathocuproine (bcp)</td>
			<td style="width:71px;">Acros</td>
			<td style="width:119px;">161340010</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Acetonitrile, 99.9+</td>
			<td style="width:71px;">Acros</td>
			<td style="width:119px;">326811000</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Celite 545</td>
			<td style="width:71px;">Acros</td>
			<td style="width:119px;">349670025</td>
			<td></td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;width:216px;">Bis[(2-diphenylphosphino)phenyl] ether (DPEphos)</td>
			<td style="width:71px;">Acros</td>
			<td style="width:119px;">383370050</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Calcium hydride</td>
			<td style="width:71px;">Acros</td>
			<td style="width:119px;">C/1620/48</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Dichloromethane, 99.8%</td>
			<td style="width:71px;">Fisher Chemical</td>
			<td style="width:119px;">D/1852/25</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Dietyl ether, &#62;= 99%</td>
			<td style="width:71px;">Fisher Chemical</td>
			<td style="width:119px;">D/2400/MS21</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Ethyl acetate</td>
			<td style="width:71px;">Fisher Chemical</td>
			<td style="width:119px;">E/0900/25</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">N-Methylpyrrole, 99%</td>
			<td style="width:71px;">Sigma Aldrich</td>
			<td style="width:119px;">M78801</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">4-Iodobenzonitrile, 98%</td>
			<td style="width:71px;">Combi-Blocks</td>
			<td style="width:119px;">OR-3151</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Petroleum ether (40-60 &#176;)</td>
			<td style="width:71px;">Fisher Chemical</td>
			<td style="width:119px;">P/1760/25</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Potassium carbonate, anhydrous</td>
			<td style="width:71px;">Fisher Chemical</td>
			<td style="width:119px;">P/4120/60</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Tetrakisacetonitrile copper(I) hexafluorophosphate, 97%</td>
			<td style="width:71px;">Sigma Aldrich</td>
			<td style="width:119px;">346276</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Equipment</td>
			<td style="width:71px;"></td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">1H and 13C NMR spectrometer</td>
			<td style="width:71px;">Bruker</td>
			<td style="width:119px;">Avance 300 Spectrometer</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">1H and 13C NMR spectrometer</td>
			<td style="width:71px;">Varian</td>
			<td style="width:119px;">VNMRS 400 Spectrometer</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">420 nm light tubes</td>
			<td style="width:71px;">Luzchem</td>
			<td style="width:119px;">LZC-420</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Blue LEDs lamp</td>
			<td style="width:71px;">Kessil</td>
			<td style="width:119px;">H150-Blue</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Blue LEDs strips</td>
			<td style="width:71px;">Eglo</td>
			<td style="width:119px;">92065</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Photochemistry Device PhotoRedOx Box</td>
			<td style="width:71px;">Hepatochem</td>
			<td style="width:119px;">HCK1006-01-016</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Photoreactor</td>
			<td style="width:71px;">Luzchem</td>
			<td style="width:119px;">CCP-4V</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Spectrofluorimeter</td>
			<td style="width:71px;">Shimadzu</td>
			<td style="width:119px;">RF-5301PC</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">UV/Vis spectrometer</td>
			<td style="width:71px;">Perkin Elmer</td>
			<td style="width:119px;">Lambda 40</td>
			<td></td>
		</tr>
	</tbody>
</table>

[(dpephos)(bcp)cu]pf6: a general and broadly applicable copper-based photoredox catalyst

我们的小组最近报告了使用 [(Dpepphos) (bcp) CU] PF6作为一般铜基光电多克斯催化剂, 证明有效地促进了多种有机卤化物的活化, 包括未激活的卤化物。然后, 它们可以参与各种自由基的转变, 如还原和环化反应, 以及几种 (异质) 芳烃的直接芳基化。这些转变提供了一个直接的访问一系列感兴趣的合成化学小分子, 以及生物活性天然产品。总之, [(Dpepphos) (bcp) CU] PF6是一种方便的光数催化剂, 它似乎是一种极具吸引力、廉价和互补的替代品, 取代了最先进的基于虹膜和红宝石的光华多波催化剂。在这里, 我们报告了一个详细的协议, 用于合成 [(dpephos) (Bcp) CU]pf 6, 以及核磁共振和光谱特征, 我们说明了它在合成化学中的应用, 用于 (杂化) 芳烃和自由基环化。有机卤化物。特别是, n-甲基吡咯与 4-碘苯并腈的直接芳化, 可承受 4-(1-甲基-1 h-吡咯-2-酰基) 苯并腈的自由环化和n-苯甲基-n-[(2-碘喹诺林 3-基) 甲基化。氰氨化物提供天然产品罗托宁 a 是详细的。简要讨论了这种铜基光毒催化剂的范围和局限性。

[(Dpepphos) (bcp) Cu] PF6的合成 如上一节所述的协议所示, [(dpepphos) (Bcp) Cu] PF6的合成特别方便, 可以很容易地在多克比例上执行。1h 和13c 核磁共振光谱表明纯复合物的形成 (图 4a, b)。光谱数据与以前报告的数据一致31。
1H 核磁共振 (400 兆赫, CDCl3) (ppm): 7.83 (s, 2h), 7.6...

Watch this Scientific Journal Video about [DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst at JoVE.com

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

本文提出了合成 [(Dpepphos) (bcp) Cu] PF6的详细和一般的协议, 这是一种普通的铜基光多克斯催化剂, 并用于合成化学中的 c-h 键在 (异种) 芳烃和自由基中的直接芳基化有机卤化物的环化。

[(Dpepphos) (bcp) Cu]PF6: 一种通用的、广泛适用的铜基光氧催化剂

Our group recently reported the use of [(DPEPhos)(bcp)Cu]PF6 as a general copper-based photoredox catalyst which proved efficient to promote the ...

在过去的十年里，光雷多克斯催化已经出现，作为促进激进过程最有效的方法之一。它确实特别容易实施，用户友好，高度可持续，而且它不依赖于使用有毒或危险的试剂，通常用于激进化学。光雷多克斯催化的主要原理非常简单，因为，正如你可以告诉的名字，它是基于使用光反应化合物称为光雷诺克斯催化剂，可以很容易地激活与可见光的辐照，以启动催化循环。在迄今报告和利用的所有光雷多克斯催化剂中，大多数催化剂实际上都基于由于价格高而造成相当强烈的限制的钛和虹膜复合物。因此，开发以铜等廉价和非贵金属金属为基础的替代光脱氧化物催化剂，不仅对于开发成本较低的系统，而且对于新的应用也非常重要。当我们开始合成和开发这种新的铜基光雷多克斯催化剂时，这是一个主要的动机，其合成与合成应用一起呈现在视频中。除了化学合成器的作用外，铜基催化剂还可以在光催化中发挥作用，例如，在减少水或减少二氧化碳方面，这对清洁能源的生产和储存以及污染也非常重要。我实验室的两名博士生哈贾尔·巴古亚女士和杰罗姆·博德洛特先生将演示这些程序。首先，在装有磁性搅拌棒的两升圆形底瓶中加入 10 毫摩尔的特塔基塞托尼特利铜（I）六氟磷酸盐和 10 毫摩尔的 DPEPhos。将圆形底部烧瓶与连接到真空管路和装满 argon 的气球连接的三颈真空适配器安装。转动适配器以疏散烧瓶一分钟，然后再次转动适配器，用砷回填烧瓶。重复此循环两次。用橡胶隔膜将三个颈部真空适配器替换为一个气孔气球。通过针头，加入800毫升的蒸馏二氯甲烷，用铝箔包裹烧瓶以阻挡光线。将烧瓶放在磁搅拌器上，在大约 23 至 25 摄氏度的气孔气氛下搅拌反应混合物两小时。之后，在装有磁性搅拌棒的500毫升圆形底部烧瓶中加入10毫摩尔的bp。将圆形底部烧瓶与连接到真空管路和装满 argon 的气球连接的三颈真空适配器安装。在真空下排空烧瓶，用砷回填三次。用橡胶隔膜将三个颈部真空适配器替换为一个气孔气球。通过针头，加入200毫升蒸馏二氯甲烷，轻轻搅拌悬浮液，直到完全溶解的bcp。将一个管套在两升和 500 毫升烧瓶上的两个橡胶隔膜上，将卡努拉的端端浸入 500 毫升烧瓶中的溶液中。从两升烧瓶中取出砷气球，将较小烧瓶的全部内容转移到更大的烧瓶中。然后，把气球放回两升的烧瓶上。在黑暗中搅拌一个小时，在大约23至25摄氏度的大气中。接下来，将一片芹菜放在烧瓶顶部的褶皱漏斗中，然后过滤混合物。用大约100毫升的蒸馏二氯甲烷清洗。然后，将烧瓶放在旋转蒸发器上，在减压下将滤液浓缩到 50 到 100 毫升之间的体积。使用添加漏斗将浓缩物滴到磁搅拌器上，用剧烈搅拌器将浓缩物滴到一升二乙醚上，从而引能所需复合物的沉淀。现在，通过过滤收集沉淀物，在布赫纳烧瓶顶部有三微米的孔径，用约 100 毫升的二乙醚清洗沉淀物。在室温下真空下干燥亮黄色沉淀物5小时，回收10.1克，相当于铜复合物91%的收益率。首先，在烤箱干燥的10毫升小瓶中，加入0.05毫摩尔的合成催化剂，0.25毫摩尔的二环甲基异丁胺，1毫摩尔的碳酸钾，和0.5毫摩尔的4-碘乙酰胺。放置磁搅拌棒。用橡胶隔膜密封小瓶。将小瓶连接到连接到真空的橡胶管路，在真空下将小瓶疏散 30 秒，然后用 argon 回填三次。然后，通过隔膜，加入五毫升的新鲜蒸馏和脱气的乙酰醇和890微升的n-甲基丙烯到小瓶。用螺钉盖更换橡胶隔膜。将小瓶放入光反应器中，在420纳米波长的辐照下，在大约23至25摄氏度下搅拌反应混合物三天。可以使用蓝色 LED 条或 440 纳米和 34 瓦的蓝色 LED 灯。三天后，通过一垫的芹铁矿过滤反应混合物。用大约五毫升的二乙醚清洗，并在旋转蒸发器上在压力下将滤液浓缩。接下来，用最小量的溶剂溶解浓缩物，并放在柱色谱的顶部，开始净化硅胶上的粗残留。之后，将含有纯产品的所有管的含量放在烧瓶中，并集中到旋转蒸发器上。将烧瓶放在真空管上，在室温下干燥纯化合物三小时，以回收 65 毫克，相当于所需 C2 丙烯酸热变的 72% 愈合。在该协议中，DPEPhos bcp铜（I）六氟磷酸盐的合成特别方便，并且可以很容易地在多图尺度上执行。质子和碳-13 NMR光谱表明纯复合物的形成。UV 和可见光吸收光谱显示两个主要吸收带，在 385 纳米和 485 纳米时具有两个最大值。在445纳米时通过激发获得的发射频谱在535纳米时显示最大。至于C2丙烯酸热耳的表征，质子和碳-13 NMR光谱表示纯化合物的形成。光催化剂可用于合成其他分子，如抗癌剂罗托宁A的完全合成，它显示了其质子和碳-13 NMR光谱所表现出的良好的纯度。需要记住的最重要的事情之一是分子氧可以被光催化剂激活并诱导侧反应。因此，所有反应都应在砷下进行，并严格排除氧气。铜基光脱氧催化剂可用于光催化的其他领域，目前正在研究其他铜复合物。光反应器发出强光，因此，只有在关上门后才小心地将其打开。此外，为了避免进一步暴露，还应佩戴紫外线过滤护目镜。

Research

JoVE Journal

Chemistry

[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

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

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

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

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

科研

化学

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

合成与盘状磷酸盐锆剥落获取胶体液晶

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

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

科大-1作为香兰素的合成的非均相催化剂

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

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

使用Photoredox催化剂蠕虫状胶束的简便合成可见光介导的分散聚合

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins ...

Peptide and Protein Quantification Using Automated Immuno-MALDI (iMALDI)

Peptide and Protein Quantification Using Automated Immuno-MALDI iMALDI

多肽和蛋白质量化使用自动免疫-MALDI (iMALDI)

Mass spectrometry (MS) is one of the most commonly used technologies for quantifying proteins in complex samples, with excellent assay specificity as a ...

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes

镍/锌配合物介导的O-Carboxyanhydrides 的控制 Photoredox 环开聚合

Here, we describe an effective protocol that combines photoredox Ni/Ir catalysis with the use of a Zn-alkoxide for efficient ring-opening polymerization, ...

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

电化学 CO2还原的过渡金属单原子催化剂的合成及性能表征

This protocol presents both the synthesis method of the Ni single atom catalyst, and the electrochemical testing of its catalytic activity and selectivity ...

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

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 ...

Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts

氧化锰催化剂光活化 Polyoxometalate 基光响应膜的制备

This paper presents a method to prepare charge-transfer chromophores using polyoxotungstate (PW12O403-), transition metal ions (Ce3+ or Co2+), and organic ...

Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics

利用密度泛函理论和力场分子动力学对多相水-金属催化剂接口进行多尺度采样

A significant number of heterogeneously-catalyzed chemical processes occur under liquid conditions, but simulating catalyst function under such conditions ...