{"id":25636,"date":"2017-09-26T07:06:39","date_gmt":"2017-09-26T14:06:39","guid":{"rendered":"https:\/\/hepatochem.com\/photoreactor-setup\/"},"modified":"2017-09-26T07:06:39","modified_gmt":"2017-09-26T14:06:39","slug":"photoreactor-setup","status":"publish","type":"post","link":"https:\/\/hepatochem.com\/euro\/photoreactor-setup\/","title":{"rendered":"PhotoReactor Setup"},"content":{"rendered":"<p><!DOCTYPE html PUBLIC \"-\/\/W3C\/\/DTD HTML 4.0 Transitional\/\/EN\" \"http:\/\/www.w3.org\/TR\/REC-html40\/loose.dtd\"><br \/>\n<html><body><\/p>\n<p>[et_pb_section fb_built=&#8221;1&#8243; _builder_version=&#8221;4.16&#8243; global_colors_info=&#8221;{}&#8221;][et_pb_row _builder_version=&#8221;4.16&#8243; background_size=&#8221;initial&#8221; background_position=&#8221;top_left&#8221; background_repeat=&#8221;repeat&#8221; global_colors_info=&#8221;{}&#8221;][et_pb_column type=&#8221;4_4&#8243; _builder_version=&#8221;4.16&#8243; custom_padding=&#8221;|||&#8221; global_colors_info=&#8221;{}&#8221; custom_padding__hover=&#8221;|||&#8221;][et_pb_text _builder_version=&#8221;4.16&#8243; background_size=&#8221;initial&#8221; background_position=&#8221;top_left&#8221; background_repeat=&#8221;repeat&#8221; global_colors_info=&#8221;{}&#8221;]Interest in photochemistry has been growing exponentially in recent years. Numerous new applications using visible-light photoredox catalysis have been discovered. These catalytic systems can perform many types of bond formations using various substrates which are valuable new tools for synthetic chemists.<\/p>\n<p>However photoredox chemistry setup necessitates to the use of a light source (blue light) and apparatus that are not standard yet in an organic chemistry laboratory. Many chemists have made their own setup and tried to reproduce literature chemistry with more or less success. As a result the implementation of photoredox chemistry is slow and organic chemists are still hesitant to try these important new tools. Therefore, the need for a simple and robust device to perform visible-light photoredox catalysis has become increasingly important.\n<\/p>\n<h3>EvoluChem&trade; PhotoRedOx Box<\/h3>\n<p>The EvoluChem&trade; PhotoRedOx Box was designed with one main objective: To allow any chemist to easily perform multiple photoredox reactions in a reproducible environment. Our photochemistry device provide an even light distribution to all reaction samples allowing consistent and reproducible reactions. A cooling fan allows even temperature distribution and keeps the chamber near room temperature during long reaction runs. The device easily fits on standard stir plates, allowing for consistent stirring. Sample holders are compatible with vials ranging from 0.3 ml to 20 ml vials.<\/p>\n<h3>Unique Design<\/h3>\n<p>The PhotoRedOx Box is using a unique geometry of mirrors to irradiate multiple samples simulatanously for parallel chemistry setup while limiting the thermal effect of the light source. This design results into a compact and efficient photoredox device which can be easely set on any standard stir plate.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-medium wp-image-2703\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2016\/12\/light_mirrors-300x260.png\" alt=\"light_mirrors\" width=\"300\" height=\"260\"><\/p>\n<p>The removable lamp adapter allows easy switching from the standard kessil&trade; blue 34W LED lamp to many other light sources.<\/p>\n<h3>Fit multiple vial formats<\/h3>\n<p>Organic chemists needs to be able to use different reaction vial sizes depending on the scale and the number of the reaction to be performed. The PhotoRedox Box can virtually fit any type of vials including 0.3ml crimped vials (6 x 32mm), 2ml HPLC vials (12 x 32mm), 1DRAM (15 x 45mm), Microwave vial 2-5mL (17 x 83mm), 2DRAM (17 x 60mm) and 20ml scintillation vials (28 x 61mm). This feature allows quick and consistent scale up from screen reactions to larger scale with preset sample positions removing the guess work on sample placement distance from the light source. When using 0.3 ml vials, 32 reactions can be performed in parallel in the photochemical device. At 20 ml, two reactions can be run in duplicate.<\/p>\n<h3>Reproducibility<\/h3>\n<p>With the EvoluChem photomethylation kit, we have demonstrated the reproducibility of both the photomethylation kit and the device. Using a photomethylation of buspirone as test reaction, 16 vials spread through the 0.3 ml vial sample holder for Trial #1 results in 53% (+\/-2 %) conversion. See figure. For a second trial with 16 reaction vials we observed an average conversion of 56% (+\/-2 %) for the mono-methylated product.<\/p>\n<p><strong>Test reaction (Methylation)<\/strong><\/p>\n<p><strong><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-large wp-image-2751\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2016\/12\/photomethylation_reaction-1024x169.png\" alt=\"photomethylation_reaction\" width=\"580\" height=\"96\"><br \/>\n<\/strong><\/p>\n<table width=\"100%\">\n<tbody>\n<tr>\n<td>\n<p style=\"text-align: center;\"><strong>Percentage of mono-methylation product<\/strong><\/p>\n<p style=\"text-align: center;\"><strong>by reaction vial position<\/strong><\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-3015\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/reproducibility_photomethylation.png\" alt=\"reproducibility_photomethylation\" width=\"411\" height=\"252\" srcset=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/reproducibility_photomethylation.png 411w, https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/reproducibility_photomethylation-300x184.png 300w\" sizes=\"(max-width: 411px) 100vw, 411px\" \/><\/p>\n<p style=\"text-align: center;\"><strong>Average- 53% +\/-2%<\/strong><\/p>\n<p>Reaction conditions:<\/p>\n<p>Each reaction vial contains Ir(dF-CF<sub>3<\/sub>-ppy)<sub>2<\/sub>(dtbpy)[PF<sub>6<\/sub>] (0.1 \u03bcmol), tert-butylperacetate solution (12.5 \u03bcmol) and a stir bar sealed under inert atmosphere. To each vial was added 50 \u03bcl of 0.05 M buspirone solution in 1:1 trifluoroacetic acid\/acetonitrile sparged with nitrogen stream. Reaction mixture irradiated with Kessil 34 W blue LED for 18 hr using EvoluChem photochemical device.<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n<h2>Ir\/Ni visible-light photoredox catalysis exploration<\/h2>\n<p>A significant number of traditional cross-coupling reactions have been performed using photochemistry. In many cases, this involves using an Iridium photocatalyst like Ir(dF-CF<sub>3<\/sub>-ppy)<sub>2<\/sub>(dtbpy)[PF<sub>6<\/sub>] to activate a sluggish catalytic cycle (Ni) in the presence of a ligand and base. Many reactions conditions have been reported in the literature using a wide range of reagents. However, often these reactions are highly substrate, solvent and base specific. We describe several examples from literature that haven been modified to be performed in kit form in our PhotoRedOx box device.<\/p>\n<h3>Screening reaction conditions<\/h3>\n<p>To reduce the amount of catalysts, reagents and substrate used during reaction screening, we perform reaction condition at 5 \u03bcmol substrate in 100 \u03bcl solvent with 0.1 \u03bcmol Ir catalyst and 0.5 \u03bcmol premixed Ni-dtbbpy with 3 equiv. of base with stir in a vial capped under inert atmosphere.<\/p>\n<h3>C-C coupling through decarboxylation<\/h3>\n<p>The decarboxylative sp3-sp2 cross-coupling of amino acids and other activated carboxylic acids with aryl halides is a powerful tool for the synthesis of new organic molecules.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-3017\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Zuo_Article.png\" alt=\"Zuo_Article\" width=\"557\" height=\"153\" srcset=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Zuo_Article.png 557w, https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Zuo_Article-300x82.png 300w\" sizes=\"(max-width: 557px) 100vw, 557px\" \/><\/p>\n<p>See Reference: Zuo, Z., et. al. <em>Science <\/em>2014, 345, 437-440.<\/p>\n<p>The success of this type of reaction relies on finding the right combination of Ir catalyst \/ Ni ligand, base and solvent. We performed the cross-coupling reaction between the substrates Boc-Val and 4-bromoacetophenone using 100 \u03bcl screening reaction condition as described previously. The results shows that the conversion is highly dependent on base. In this case Cs<sub>2<\/sub>CO<sub>3<\/sub> and K<sub>3<\/sub>PO<sub>4<\/sub> promote the reaction while DABCO and DBU do not.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-3024\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/BocVal_Cs2CO3.png\" alt=\"BocVal_Cs2CO3\" width=\"609\" height=\"138\" srcset=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/BocVal_Cs2CO3.png 609w, https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/BocVal_Cs2CO3-600x136.png 600w, https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/BocVal_Cs2CO3-300x68.png 300w\" sizes=\"(max-width: 609px) 100vw, 609px\" \/><\/p>\n<h3>C-N coupling with secondary amines<\/h3>\n<p>Cross-coupling reaction between halide aryl and secondary amine aliphatic amine are possible with Ir\/Ni photoredox catalysis.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-3023\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/corcoron_article.png\" alt=\"corcoron_article\" width=\"558\" height=\"155\" srcset=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/corcoron_article.png 558w, https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/corcoron_article-300x83.png 300w\" sizes=\"(max-width: 558px) 100vw, 558px\" \/><\/p>\n<p>See reference: Corcoron, E. <em>et. al., Science <\/em>2016, 353, 279-283.<\/p>\n<p>Like decarboxylative sp3-sp2 cross-coupling, the success of this C-N cross-coupling relies on finding the right combination of Ir catalyst \/ Ni ligand, base and solvent. For example the cross-coupling reaction between the substrates pyrolidine and 4-bromoacetophenone (see below) is highly dependent of the used base. In that case DABCO promotes the reaction when Cs<sub>2<\/sub>CO<sub>3<\/sub>, K<sub>3<\/sub>PO<sub>4<\/sub> and DBU don&#8217;t.<\/p>\n<p><strong><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-3022\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/pyrolidine_dabco.png\" alt=\"pyrolidine_dabco\" width=\"594\" height=\"147\" srcset=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/pyrolidine_dabco.png 594w, https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/pyrolidine_dabco-300x74.png 300w\" sizes=\"(max-width: 594px) 100vw, 594px\" \/><\/strong><\/p>\n<h3>C-N coupling with aromatic amines<\/h3>\n<p>Cross-coupling reaction between halide aryl and aromatic amine are possible with Ir\/Ni photoredox catalysis.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-3021\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Oderinde_article.png\" alt=\"Oderinde_article\" width=\"558\" height=\"155\" srcset=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Oderinde_article.png 558w, https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Oderinde_article-300x83.png 300w\" sizes=\"(max-width: 558px) 100vw, 558px\" \/><\/p>\n<p>See reference: Oderinde, M., <em>et. al. Angew. Chemie, <\/em>2016, 55, 13219-13223<\/p>\n<p>In that case aniline and 4-bromoacetophenone are reacting in presence of DBU or DABCO.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-3020\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Aniline_DBU.png\" alt=\"Aniline_DBU\" width=\"594\" height=\"147\" srcset=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Aniline_DBU.png 594w, https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Aniline_DBU-300x74.png 300w\" sizes=\"(max-width: 594px) 100vw, 594px\" \/><\/p>\n<h3>C-N coupling with secondary and aromatic amines<\/h3>\n<p>With the indoline as substrate the reaction works better with K<sub>3<\/sub>PO<sub>4<\/sub>.<strong><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-3019\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Indole_k3po4.png\" alt=\"Indole_k3po4\" width=\"595\" height=\"147\" srcset=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Indole_k3po4.png 595w, https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Indole_k3po4-300x74.png 300w\" sizes=\"(max-width: 595px) 100vw, 595px\" \/><\/strong><\/p>\n<h3>Results summary<\/h3>\n<p>Selection of base and solvent important to find condition for appropriate coupling (5 \u03bcmol per reaction \/100 \u03bcL scale)<\/p>\n<h3>Screen Reaction 20x Scale-up<\/h3>\n<p>Reaction condition identified in the screen can be directly transposed to larger scale. For example the The decarboxylative sp3-sp2 cross-coupling of Boc-Val and 4-bromoacetophenone can be scaled up from 5 \u03bcmol to 100 \u03bcmol with 90% conversion.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-3018\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/bocvalscaleup.png\" alt=\"bocvalscaleup\" width=\"571\" height=\"147\" srcset=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/bocvalscaleup.png 571w, https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/bocvalscaleup-300x77.png 300w\" sizes=\"(max-width: 571px) 100vw, 571px\" \/><strong>Experimental Details: <\/strong>In duplicate in a 4-ml vial equipped with a teflon septa and 2&#215;7 mm stir bar, were weighed NiCl<sub>2<\/sub>-dme (2.2 mg, 10 \u03bcmol, 0.1 mol %), dtbbpy (2.68 mg, 10 \u03bcmol, 0.1 mol %), Ir(dF-CF3-ppy)<sub>2<\/sub>(dtbpy) (2.24 mg, 2 \u03bcmol, 0.02 mol %), and Cs<sub>2<\/sub>CO<sub>3 <\/sub>(97.8 mg, 300 \u03bcmol, 3 equiv.). To this vial was added a 2.0 ml solution in DMF containing Boc-Val-OH (10.85 mg, 100 \u03bcmol, 1 equiv.) and 4-bromoacetophenone (9.95 mg, 100 \u03bcmol, 1 equiv.). The solution was sparged with nitrogen via submerged needle for 5 minutes and vial was placed in EvoluChem PhotoRedOx Box with blue Kessil LED and irradiated for 24 hrs. Reaction progress was monitored by LC-MS. After 24 hours, conversion was greater than 90%. No additional product was observed at 48 hrs.<strong><br \/>\n<\/strong><\/p>\n<h2>Iridium\/Nickel Photoredox Kits<\/h2>\n<p>In order to facilitate the screening of common photochemistry reactions, EvoluChem has released a series of kits combining common Iridium, nickel, ligand and base combinations to achieve the following transformations.<\/p>\n<h3>Ir\/Ni base and solvent screen kit: HCK1009-01-002<\/h3>\n<p>This kit is designed to screen reaction conditions with 8 different bases, Iridium catalyst Ir(dF-CF<sub>3<\/sub>-ppy)<sub>2<\/sub>(dtbbpy)[PF<sub>6<\/sub>] and Ni ligand dtbbpy. This is the quickest way to find which base will work with your substrates.<\/p>\n<p><strong>Kit reagent map<\/strong><\/p>\n<table style=\"border: 1px solid black;\">\n<tbody>\n<tr style=\"border: 1px solid black;\">\n<td style=\"border: 1px solid black;\" width=\"61\"><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"61\"><strong>Cs<\/strong><strong><sub>2<\/sub><\/strong><strong>CO<\/strong><strong><sub>3<\/sub><\/strong><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"61\"><strong>K<\/strong><strong><sub>3<\/sub><\/strong><strong>PO<\/strong><strong><sub>4<\/sub><\/strong><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"57\"><strong>K<\/strong><strong><sub>2<\/sub><\/strong><strong>HPO<\/strong><strong><sub>4<\/sub><\/strong><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"61\"><strong>KOH<\/strong><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"61\"><strong>Li<\/strong><strong><sub>2<\/sub><\/strong><strong>CO<\/strong><strong><sub>3<\/sub><\/strong><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"61\"><strong>K<\/strong><strong><sub>2<\/sub><\/strong><strong>CO<\/strong><strong><sub>3<\/sub><\/strong><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"61\"><strong>DABCO<\/strong><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"61\"><strong>DBU<\/strong><\/td>\n<\/tr>\n<tr style=\"border: 1px solid black;\">\n<td style=\"border: 1px solid black;\" width=\"61\">Solvent A<\/td>\n<td colspan=\"8\" rowspan=\"2\" width=\"484\">\n<p style=\"text-align: center;\">2 sets of 8 bases per kit (16 total vials)<\/p>\n<p style=\"text-align: center;\">HCK1009-01-002<\/p>\n<\/td>\n<\/tr>\n<tr>\n<td style=\"border: 1px solid black;\" width=\"61\">Solvent B<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n<p><strong><\/strong><\/p>\n<h3>Ir\/Ni base and ligand screen kits:<\/h3>\n<h3>HCK1009-01-003\/ HCK1009-01-004<\/h3>\n<p>This kit is designed to screen both bases and Ni Ligand with Iridium catalyst Ir(dF-CF<sub>3<\/sub>-ppy)<sub>2<\/sub>(dtbbpy)[PF<sub>6<\/sub>].<\/p>\n<p>It is recommended for difficult or complex substrates.<\/p>\n<table width=\"0\">\n<tbody>\n<tr style=\"border: 1px solid black;\">\n<td style=\"border: 1px solid black;\" width=\"50\"><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>Cs<sub>2<\/sub>CO<sub>3<\/sub><\/strong><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>K<sub>3<\/sub>PO<sub>4<\/sub><\/strong><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>K<sub>2<\/sub>HPO<sub>4<\/sub><\/strong><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>K<sub>2<\/sub>CO<sub>3<\/sub><\/strong><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>DABCO<\/strong><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>DBU<\/strong><\/td>\n<\/tr>\n<tr style=\"border: 1px solid black;\">\n<td style=\"border: 1px solid black;\" width=\"80\"><strong>dtbbpy<\/strong><\/td>\n<td colspan=\"4\" rowspan=\"4\">\n<p style=\"text-align: center;\">2 sets of 4 bases and 4 ligands per kit<\/p>\n<p style=\"text-align: center;\">(32 total vials)<\/p>\n<p style=\"text-align: center;\">HCK1009-01-003<\/p>\n<\/td>\n<td style=\"border: 1px solid black;\" colspan=\"2\" rowspan=\"4\" width=\"151\">\n<p style=\"text-align: center;\">2 sets of 6 bases<\/p>\n<p style=\"text-align: center;\">and 4 ligands per kit<\/p>\n<p style=\"text-align: center;\">(48 total vials)<\/p>\n<p style=\"text-align: center;\">HCK1009-01-004<\/p>\n<\/td>\n<\/tr>\n<tr style=\"border: 1px solid black;\">\n<td style=\"border: 1px solid black;\" width=\"80\"><strong>bphen<\/strong><\/td>\n<\/tr>\n<tr style=\"border: 1px solid black;\">\n<td style=\"border: 1px solid black;\" width=\"80\"><strong>(MeO)<sub>2<\/sub>bpy<\/strong><\/td>\n<\/tr>\n<tr style=\"border: 1px solid black;\">\n<td style=\"border: 1px solid black;\" width=\"80\"><strong>biox<\/strong><\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n<p><strong><\/strong><\/p>\n<p><strong><\/strong><\/p>\n<h3 id=\"005\">Ir\/Ni base and Ir catalyst screen kit: HCK1009-01-005<\/h3>\n<p>This kit is designed to screen both bases (3) and Iridium catalysts (6) with Ni Ligand.<\/p>\n<p>It is recommended for difficult or complex substrates.<\/p>\n<table width=\"0\">\n<tbody>\n<tr style=\"border: 1px solid black; height: 25px;\">\n<td style=\"border: 1px solid black;\" width=\"200\"><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>Cs<sub>2<\/sub>CO<sub>3<\/sub><\/strong><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>CsF<\/strong><\/td>\n<td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>DBU<\/strong><\/td>\n<\/tr>\n<tr style=\"border: 1px solid black; height: 25px;\">\n<td style=\"border: 1px solid black;\" width=\"200\"><strong>Ir(dF-CF<sub>3<\/sub>-ppy)<sub>2<\/sub>(dtbbpy)PF<sub>6<\/sub><\/strong><\/td>\n<td style=\"border: 1px solid black;\" colspan=\"3\" rowspan=\"6\" width=\"263\">\n<p style=\"text-align: center;\">2 sets of 3 bases and 6 Ir catalysts per kit<\/p>\n<p style=\"text-align: center;\">(36 total vials)<\/p>\n<p style=\"text-align: center;\">HCK1009-01-005<\/p>\n<\/td>\n<\/tr>\n<tr style=\"border: 1px solid black; height: 25px;\">\n<td style=\"border: 1px solid black;\" width=\"200\"><strong>Ir(dtbbpy)(ppy)<sub>2<\/sub>PF<sub>6<\/sub><\/strong><\/td>\n<\/tr>\n<tr style=\"border: 1px solid black; height: 25px;\">\n<td style=\"border: 1px solid black;\" width=\"200\"><strong>Ir(dF-CF<sub>3<\/sub>-ppy)<sub>2<\/sub>(bpy)PF<sub>6<\/sub><\/strong><\/td>\n<\/tr>\n<tr style=\"border: 1px solid black; height: 25px;\">\n<td style=\"border: 1px solid black;\" width=\"200\"><strong>Ir(dF-ppy)<sub>3<\/sub><\/strong><\/td>\n<\/tr>\n<tr style=\"border: 1px solid black; height: 25px;\">\n<td style=\"border: 1px solid black;\" width=\"200\"><strong>Ir(dmppy)<sub>2<\/sub>(dtbbpy)PF<sub>6<\/sub><\/strong><\/td>\n<\/tr>\n<tr style=\"border: 1px solid black; height: 25px;\">\n<td style=\"border: 1px solid black;\" width=\"200\"><strong>Ir(dF-CH<sub>3<\/sub>-ppy)<sub>2<\/sub>(dtbbpy)PF<sub>6<\/sub><\/strong><\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n<p>[\/et_pb_text][\/et_pb_column][\/et_pb_row][\/et_pb_section]<\/body><\/html><\/p>\n","protected":false},"excerpt":{"rendered":"<p>The need for a simple and robust device to perform visible-light photoredox catalysis has become increasingly important. Learn about our setup.<\/p>\n","protected":false},"author":1,"featured_media":25060,"comment_status":"closed","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_et_pb_use_builder":"on","_et_pb_old_content":"<p>Interest in photochemistry has been growing exponentially in recent years. Numerous new applications using visible-light photoredox catalysis have been discovered. These catalytic systems can perform many types of bond formations using various substrates which are valuable new tools for synthetic chemists.<\/p><p>However photoredox chemistry setup necessitates to the use of a light source (blue light) and apparatus that are not standard yet in an organic chemistry laboratory. Many chemists have made their own setup and tried to reproduce literature chemistry with more or less success. As a result the implementation of photoredox chemistry is slow and organic chemists are still hesitant to try these important new tools. Therefore, the need for a simple and robust device to perform visible-light photoredox catalysis has become increasingly important.<\/p><h3>EvoluChem\u2122 PhotoRedOx Box<\/h3><p>The EvoluChem\u2122 PhotoRedOx Box was designed with one main objective: To allow any chemist to easily perform multiple photoredox reactions in a reproducible environment. Our photochemistry device provide an even light distribution to all reaction samples allowing consistent and reproducible reactions. A cooling fan allows even temperature distribution and keeps the chamber near room temperature during long reaction runs.\u00a0 The device easily fits on standard stir plates, allowing for consistent stirring.\u00a0\u00a0\u00a0 Sample holders are compatible with vials ranging from 0.3 ml to 20 ml vials.<\/p><h3>Unique Design<\/h3><p>The PhotoRedOx Box is using a unique geometry of mirrors to irradiate multiple samples simulatanously for parallel chemistry setup while limiting the thermal effect of the light source. This design results into a compact and efficient photoredox device which can be easely set on any standard stir plate.<\/p><p><img class=\"aligncenter size-medium wp-image-2703\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2016\/12\/light_mirrors-300x260.png\" alt=\"light_mirrors\" width=\"300\" height=\"260\" \/><\/p><p>The removable lamp adapter allows easy switching from the standard kessil\u2122 blue 34W LED lamp to many other light sources.<\/p><h3>Fit multiple vial formats<\/h3><p>Organic chemists needs to be able to use different reaction vial sizes depending on the scale and the number of the reaction to be performed. The PhotoRedox Box can virtually fit any type of vials including 0.3ml crimped vials (6 x 32mm), 2ml HPLC vials (12 x 32mm), 1DRAM (15 x 45mm), Microwave vial 2-5mL (17 x 83mm), 2DRAM (17 x 60mm) and 20ml scintillation vials (28 x 61mm). This feature allows quick and consistent scale up from screen reactions to larger scale with preset sample positions removing the guess work on sample placement distance from the light source.\u00a0\u00a0 When using 0.3 ml vials, 32 reactions can be performed in parallel in the photochemical device.\u00a0 At 20 ml, two reactions can be run in duplicate.<\/p><h3>Reproducibility<\/h3><p>With the EvoluChem photomethylation kit, we have demonstrated the reproducibility of both the photomethylation kit and the device.\u00a0 Using a photomethylation of buspirone as test reaction, 16 vials spread through the 0.3 ml vial sample holder for Trial #1 results in 53% (+\/-2 %) conversion. See figure.\u00a0 For a second trial with 16 reaction vials we observed an average conversion of 56% (+\/-2 %) for the mono-methylated product.<\/p><p><strong>Test reaction (Methylation)<\/strong><\/p><p><strong>\u00a0<img class=\"aligncenter size-large wp-image-2751\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2016\/12\/photomethylation_reaction-1024x169.png\" alt=\"photomethylation_reaction\" width=\"580\" height=\"96\" \/><br \/><\/strong><\/p><table width=\"100%\"><tbody><tr><td><p style=\"text-align: center;\"><strong>Percentage of mono-methylation product<\/strong><\/p><p style=\"text-align: center;\"><strong>by reaction vial position<\/strong><\/p><p><img class=\"aligncenter size-full wp-image-3015\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/reproducibility_photomethylation.png\" alt=\"reproducibility_photomethylation\" width=\"411\" height=\"252\" \/><\/p><p style=\"text-align: center;\"><strong>Average- 53% +\/-2%<\/strong><\/p><p>Reaction conditions:<\/p><p>Each reaction vial contains Ir(dF-CF<sub>3<\/sub>-ppy)<sub>2<\/sub>(dtbpy)[PF<sub>6<\/sub>] (0.1 \u00b5mol), tert-butylperacetate solution (12.5 \u00b5mol) and a stir bar sealed under inert atmosphere.\u00a0 To each vial was added 50 \u00b5l of 0.05 M buspirone solution in 1:1 trifluoroacetic acid\/acetonitrile sparged with nitrogen stream.\u00a0 Reaction mixture irradiated with Kessil 34 W blue LED for 18 hr using EvoluChem photochemical device.<\/p><\/td><\/tr><\/tbody><\/table><h2>Ir\/Ni visible-light photoredox catalysis exploration<\/h2><p>A significant number of traditional cross-coupling reactions have been performed using photochemistry.\u00a0 In many cases, this involves using an Iridium photocatalyst like Ir(dF-CF<sub>3<\/sub>-ppy)<sub>2<\/sub>(dtbpy)[PF<sub>6<\/sub>] to activate a sluggish catalytic cycle (Ni) in the presence of a ligand and base.\u00a0 Many reactions conditions have been reported in the literature using a wide range of reagents.\u00a0 However, often these reactions are highly substrate, solvent and base specific. We describe several examples from literature that haven been modified to be performed in kit form in our PhotoRedOx box device.<\/p><h3>Screening reaction conditions<\/h3><p>To reduce the amount of catalysts, reagents and substrate used during reaction screening, we perform reaction condition at 5 \u00b5mol substrate in 100 \u00b5l solvent with 0.1 \u00b5mol Ir catalyst and 0.5 \u00b5mol premixed Ni-dtbbpy with 3 equiv. of base with stir in a vial capped under inert atmosphere.<\/p><h3>C-C coupling through decarboxylation<\/h3><p>The decarboxylative sp3-sp2 cross-coupling of amino acids and other activated carboxylic acids with aryl halides is a powerful tool for the synthesis of new organic molecules.<\/p><p><img class=\"aligncenter size-full wp-image-3017\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Zuo_Article.png\" alt=\"Zuo_Article\" width=\"557\" height=\"153\" \/><\/p><p>See Reference:\u00a0 Zuo, Z., et. al. <em>Science <\/em>\u00a02014, 345, 437-440.<\/p><p>The success of this type of reaction relies on finding the right combination of Ir catalyst \/ Ni ligand, base and solvent. We performed the cross-coupling reaction between the substrates Boc-Val and 4-bromoacetophenone using 100 \u00b5l screening reaction condition as described previously. The results shows that the conversion is highly dependent on base. In this case Cs<sub>2<\/sub>CO<sub>3<\/sub> and K<sub>3<\/sub>PO<sub>4<\/sub> promote the reaction while DABCO and DBU do not.<\/p><p><img class=\"aligncenter size-full wp-image-3024\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/BocVal_Cs2CO3.png\" alt=\"BocVal_Cs2CO3\" width=\"609\" height=\"138\" \/><\/p><h3>C-N coupling with secondary amines<\/h3><p>Cross-coupling reaction between halide aryl and secondary amine aliphatic amine are possible with Ir\/Ni photoredox catalysis.<\/p><p><img class=\"aligncenter size-full wp-image-3023\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/corcoron_article.png\" alt=\"corcoron_article\" width=\"558\" height=\"155\" \/><\/p><p>See reference:\u00a0 Corcoron, E. <em>et. al., Science <\/em>2016, 353, 279-283.<\/p><p>Like decarboxylative sp3-sp2 cross-coupling, the success of this C-N cross-coupling relies on finding the right combination of Ir catalyst \/ Ni ligand, base and solvent. For example the cross-coupling reaction between the substrates pyrolidine and 4-bromoacetophenone (see below) is highly dependent of the used base. In that case DABCO promotes the reaction when Cs<sub>2<\/sub>CO<sub>3<\/sub>, K<sub>3<\/sub>PO<sub>4<\/sub> and DBU don\u2019t.<\/p><p><strong>\u00a0<img class=\"aligncenter size-full wp-image-3022\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/pyrolidine_dabco.png\" alt=\"pyrolidine_dabco\" width=\"594\" height=\"147\" \/><\/strong><\/p><h3>C-N coupling with aromatic amines<\/h3><p>Cross-coupling reaction between halide aryl and aromatic amine are possible with Ir\/Ni photoredox catalysis.<\/p><p><img class=\"aligncenter size-full wp-image-3021\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Oderinde_article.png\" alt=\"Oderinde_article\" width=\"558\" height=\"155\" \/><\/p><p>See reference:\u00a0 Oderinde, M., <em>et. al. Angew. Chemie, <\/em>2016, 55, 13219-13223<\/p><p>In that case aniline and 4-bromoacetophenone are reacting in presence of DBU or DABCO.<\/p><p><img class=\"aligncenter size-full wp-image-3020\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Aniline_DBU.png\" alt=\"Aniline_DBU\" width=\"594\" height=\"147\" \/><\/p><h3>C-N coupling with secondary and aromatic amines<\/h3><p>With the indoline as substrate the reaction works better with K<sub>3<\/sub>PO<sub>4<\/sub>.<strong>\u00a0<img class=\"aligncenter size-full wp-image-3019\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/Indole_k3po4.png\" alt=\"Indole_k3po4\" width=\"595\" height=\"147\" \/><\/strong><\/p><h3>Results summary<\/h3><p>Selection of base and solvent important to find condition for appropriate coupling (5 \u00b5mol per reaction \/100 \u00b5L scale)<\/p><h3>Screen Reaction 20x Scale-up<\/h3><p>Reaction condition identified in the screen can be directly transposed to larger scale. For example the The decarboxylative sp3-sp2 cross-coupling of Boc-Val and 4-bromoacetophenone can be scaled up from 5 \u00b5mol to 100 \u00b5mol with 90% conversion.<\/p><p><img class=\"aligncenter size-full wp-image-3018\" src=\"https:\/\/hepatochem.com\/wp-content\/uploads\/2017\/09\/bocvalscaleup.png\" alt=\"bocvalscaleup\" width=\"571\" height=\"147\" \/><strong>Experimental Details:\u00a0 <\/strong>In duplicate in a 4-ml vial equipped with a teflon septa and 2x7 mm stir bar, were weighed NiCl<sub>2<\/sub>-dme (2.2 mg, 10 \u00b5mol, 0.1 mol %), dtbbpy (2.68 mg, 10 \u00b5mol, 0.1 mol %), Ir(dF-CF3-ppy)<sub>2<\/sub>(dtbpy) (2.24 mg, 2 \u00b5mol, 0.02 mol %),\u00a0 and Cs<sub>2<\/sub>CO<sub>3 <\/sub>\u00a0(97.8 mg, 300 \u00b5mol, 3 equiv.). To this vial was added a 2.0 ml solution in DMF containing Boc-Val-OH (10.85 mg, 100 \u00b5mol, 1 equiv.) and 4-bromoacetophenone (9.95 mg, 100 \u00b5mol, 1 equiv.).\u00a0 The solution was sparged with nitrogen via submerged needle for 5 minutes and vial was placed in EvoluChem PhotoRedOx Box with blue Kessil LED and irradiated for 24 hrs.\u00a0 Reaction progress was monitored by LC-MS.\u00a0 After 24 hours, conversion was greater than 90%.\u00a0 No additional product was observed at 48 hrs.<strong><br \/><\/strong><\/p><h2>Iridium\/Nickel Photoredox Kits<\/h2><p>In order to facilitate the screening of common photochemistry reactions, EvoluChem has released a series of kits combining common Iridium, nickel, ligand and base combinations to achieve the following transformations.<\/p><h3>Ir\/Ni base and solvent screen kit: HCK1009-01-002<\/h3><p>This kit is designed to screen reaction conditions with 8 different bases, Iridium catalyst Ir(dF-CF<sub>3<\/sub>-ppy)<sub>2<\/sub>(dtbbpy)[PF<sub>6<\/sub>] and Ni ligand dtbbpy. This is the quickest way to find which base will work with your substrates.<\/p><p><strong>Kit reagent map<\/strong><\/p><table style=\"border: 1px solid black;\"><tbody><tr style=\"border: 1px solid black;\"><td style=\"border: 1px solid black;\" width=\"61\">\u00a0<\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"61\"><strong>Cs<\/strong><strong><sub>2<\/sub><\/strong><strong>CO<\/strong><strong><sub>3<\/sub><\/strong><\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"61\"><strong>K<\/strong><strong><sub>3<\/sub><\/strong><strong>PO<\/strong><strong><sub>4<\/sub><\/strong><\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"57\"><strong>K<\/strong><strong><sub>2<\/sub><\/strong><strong>HPO<\/strong><strong><sub>4<\/sub><\/strong><\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"61\"><strong>KOH<\/strong><\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"61\"><strong>Li<\/strong><strong><sub>2<\/sub><\/strong><strong>CO<\/strong><strong><sub>3<\/sub><\/strong><\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"61\"><strong>K<\/strong><strong><sub>2<\/sub><\/strong><strong>CO<\/strong><strong><sub>3<\/sub><\/strong><\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"61\"><strong>DABCO<\/strong><\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"61\"><strong>DBU<\/strong><\/td><\/tr><tr style=\"border: 1px solid black;\"><td style=\"border: 1px solid black;\" width=\"61\">Solvent A<\/td><td colspan=\"8\" rowspan=\"2\" width=\"484\"><p style=\"text-align: center;\">2 sets of 8 bases per kit (16 total vials)<\/p><p style=\"text-align: center;\">HCK1009-01-002<\/p><\/td><\/tr><tr><td style=\"border: 1px solid black;\" width=\"61\">Solvent B<\/td><\/tr><\/tbody><\/table><p><strong>\u00a0<\/strong><\/p><h3>Ir\/Ni base and ligand screen kits:<\/h3><h3>HCK1009-01-003\/ HCK1009-01-004<\/h3><p>This kit is designed to screen both bases and Ni Ligand with Iridium catalyst Ir(dF-CF<sub>3<\/sub>-ppy)<sub>2<\/sub>(dtbbpy)[PF<sub>6<\/sub>].<\/p><p>It is recommended for difficult or complex substrates.<\/p><table width=\"0\"><tbody><tr style=\"border: 1px solid black;\"><td style=\"border: 1px solid black;\" width=\"50\">\u00a0<\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>Cs<sub>2<\/sub>CO<sub>3<\/sub><\/strong><\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>K<sub>3<\/sub>PO<sub>4<\/sub><\/strong><\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>K<sub>2<\/sub>HPO<sub>4<\/sub><\/strong><\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>K<sub>2<\/sub>CO<sub>3<\/sub><\/strong><\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>DABCO<\/strong><\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>DBU<\/strong><\/td><\/tr><tr style=\"border: 1px solid black;\"><td style=\"border: 1px solid black;\" width=\"80\"><strong>dtbbpy<\/strong><\/td><td colspan=\"4\" rowspan=\"4\"><p style=\"text-align: center;\">2 sets of 4 bases and 4 ligands per kit<\/p><p style=\"text-align: center;\">(32 total vials)<\/p><p style=\"text-align: center;\">HCK1009-01-003<\/p><\/td><td style=\"border: 1px solid black;\" colspan=\"2\" rowspan=\"4\" width=\"151\"><p style=\"text-align: center;\">2 sets of 6 bases<\/p><p style=\"text-align: center;\">and 4 ligands per kit<\/p><p style=\"text-align: center;\">(48 total vials)<\/p><p style=\"text-align: center;\">HCK1009-01-004<\/p><\/td><\/tr><tr style=\"border: 1px solid black;\"><td style=\"border: 1px solid black;\" width=\"80\"><strong>bphen<\/strong><\/td><\/tr><tr style=\"border: 1px solid black;\"><td style=\"border: 1px solid black;\" width=\"80\"><strong>(MeO)<sub>2<\/sub>bpy<\/strong><\/td><\/tr><tr style=\"border: 1px solid black;\"><td style=\"border: 1px solid black;\" width=\"80\"><strong>biox<\/strong><\/td><\/tr><\/tbody><\/table><p><strong>\u00a0<\/strong><\/p><p><strong>\u00a0<\/strong><\/p><h3 id=\"005\">Ir\/Ni base and Ir catalyst screen kit: HCK1009-01-005<\/h3><p>This kit is designed to screen both bases (3) and Iridium catalysts (6) with Ni Ligand.<\/p><p>It is recommended for difficult or complex substrates.<\/p><table width=\"0\"><tbody><tr style=\"border: 1px solid black; height: 25px;\"><td style=\"border: 1px solid black;\" width=\"200\">\u00a0<\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>Cs<sub>2<\/sub>CO<sub>3<\/sub><\/strong><\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>CsF<\/strong><\/td><td style=\"border: 1px solid black; text-align: center;\" width=\"50\"><strong>DBU<\/strong><\/td><\/tr><tr style=\"border: 1px solid black; height: 25px;\"><td style=\"border: 1px solid black;\" width=\"200\"><strong>Ir(dF-CF<sub>3<\/sub>-ppy)<sub>2<\/sub>(dtbbpy)PF<sub>6<\/sub><\/strong><\/td><td style=\"border: 1px solid black;\" colspan=\"3\" rowspan=\"6\" width=\"263\"><p style=\"text-align: center;\">2 sets of 3 bases and 6 Ir catalysts per kit<\/p><p style=\"text-align: center;\">(36 total vials)<\/p><p style=\"text-align: center;\">HCK1009-01-005<\/p><\/td><\/tr><tr style=\"border: 1px solid black; height: 25px;\"><td style=\"border: 1px solid black;\" width=\"200\"><strong>Ir(dtbbpy)(ppy)<sub>2<\/sub>PF<sub>6<\/sub><\/strong><\/td><\/tr><tr style=\"border: 1px solid black; height: 25px;\"><td style=\"border: 1px solid black;\" width=\"200\"><strong>\u00a0Ir(dF-CF<sub>3<\/sub>-ppy)<sub>2<\/sub>(bpy)PF<sub>6<\/sub><\/strong><\/td><\/tr><tr style=\"border: 1px solid black; height: 25px;\"><td style=\"border: 1px solid black;\" width=\"200\"><strong>Ir(dF-ppy)<sub>3<\/sub><\/strong><\/td><\/tr><tr style=\"border: 1px solid black; height: 25px;\"><td style=\"border: 1px solid black;\" width=\"200\"><strong>Ir(dmppy)<sub>2<\/sub>(dtbbpy)PF<sub>6<\/sub><\/strong><\/td><\/tr><tr style=\"border: 1px solid black; height: 25px;\"><td style=\"border: 1px solid black;\" width=\"200\"><strong>Ir(dF-CH<sub>3<\/sub>-ppy)<sub>2<\/sub>(dtbbpy)PF<sub>6<\/sub><\/strong><\/td><\/tr><\/tbody><\/table>","_et_gb_content_width":"","_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":false,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_feature_clip_id":0,"_jetpack_memberships_contains_paid_content":false,"footnotes":"","jetpack_post_was_ever_published":false},"categories":[677,675,680,678],"tags":[],"class_list":["post-25636","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-educational","category-feature-2","category-featured-articles","category-photoredox"],"yoast_head":"<!-- This site is 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