Maite Molins, Javier Fernandez-Garcia and Xavier Berzosa*,
{"title":"A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl Bromides","authors":"Maite Molins, Javier Fernandez-Garcia and Xavier Berzosa*, ","doi":"10.1021/acs.oprd.4c0040210.1021/acs.oprd.4c00402","DOIUrl":null,"url":null,"abstract":"<p >Copper coil flow reactors represent an economic, abundant, and durable platform for conducting copper-catalyzed reactions. These have been used in the past for Ullmann-type reactions starting from aryl iodides. However, no procedures have been described for the activation of less reactive aryl bromides. In this work, we successfully developed a method for the hydroxylation of aryl bromides promoted by a copper coil reactor. Notably, the presence of both a diamine ligand and DMF is key for the reaction to proceed. An inorganic base such as Na<sub>2</sub>CO<sub>3</sub> also improved the reaction yield by minimizing the formation of side products. The setup has been applied to a range of disubstituted aryl bromides in moderate to good yields and was tested under 24 h of continuous operation, showing stable yields, thus proving the robustness of the catalysis. Finally, the lifetime of a copper reactor operating under the described conditions has been calculated for the first time, proving that this technology is safe to operate at an industrial scale.</p>","PeriodicalId":55,"journal":{"name":"Organic Process Research & Development","volume":"28 12","pages":"4477–4484 4477–4484"},"PeriodicalIF":3.1000,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.oprd.4c00402","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Process Research & Development","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.oprd.4c00402","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl Bromides
Copper coil flow reactors represent an economic, abundant, and durable platform for conducting copper-catalyzed reactions. These have been used in the past for Ullmann-type reactions starting from aryl iodides. However, no procedures have been described for the activation of less reactive aryl bromides. In this work, we successfully developed a method for the hydroxylation of aryl bromides promoted by a copper coil reactor. Notably, the presence of both a diamine ligand and DMF is key for the reaction to proceed. An inorganic base such as Na2CO3 also improved the reaction yield by minimizing the formation of side products. The setup has been applied to a range of disubstituted aryl bromides in moderate to good yields and was tested under 24 h of continuous operation, showing stable yields, thus proving the robustness of the catalysis. Finally, the lifetime of a copper reactor operating under the described conditions has been calculated for the first time, proving that this technology is safe to operate at an industrial scale.
期刊介绍：
The journal Organic Process Research & Development serves as a communication tool between industrial chemists and chemists working in universities and research institutes. As such, it reports original work from the broad field of industrial process chemistry but also presents academic results that are relevant, or potentially relevant, to industrial applications. Process chemistry is the science that enables the safe, environmentally benign and ultimately economical manufacturing of organic compounds that are required in larger amounts to help address the needs of society. Consequently, the Journal encompasses every aspect of organic chemistry, including all aspects of catalysis, synthetic methodology development and synthetic strategy exploration, but also includes aspects from analytical and solid-state chemistry and chemical engineering, such as work-up tools，process safety, or flow-chemistry. The goal of development and optimization of chemical reactions and processes is their transfer to a larger scale; original work describing such studies and the actual implementation on scale is highly relevant to the journal. However, studies on new developments from either industry, research institutes or academia that have not yet been demonstrated on scale, but where an industrial utility can be expected and where the study has addressed important prerequisites for a scale-up and has given confidence into the reliability and practicality of the chemistry, also serve the mission of OPR&D as a communication tool between the different contributors to the field.
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