Pub Date : 2023-01-12DOI: 10.1007/s41981-022-00256-8
Bi Bali Judicaël Tra, Abollé Abollé, Killian Lucas, François-Xavier Felpin
Herein, we report the first continuous-flow biomimetic cyclization of reticuline derivatives to aporphine alkaloids via ortho-quinol intermediates. The two-step flow process involves an initial oxidative dearomatization of reticuline derivatives to using hypervalent iodine(III) reagents, followed by a TMSOTf-mediated electrophilic cyclization. The high sensitivity of ortho-quinol compounds is mitigated by the mild experimental conditions and fast reaction rates offered by flow reactors. A preliminary structure–reactivity relationship suggests that both steps of the process are favored with strongly electron-rich substrates, similar to what is observed in nature.
{"title":"Electrophilic cyclization of reticuline-type alkaloids in flow via o-quinol intermediates","authors":"Bi Bali Judicaël Tra, Abollé Abollé, Killian Lucas, François-Xavier Felpin","doi":"10.1007/s41981-022-00256-8","DOIUrl":"10.1007/s41981-022-00256-8","url":null,"abstract":"<p>Herein, we report the first continuous-flow biomimetic cyclization of reticuline derivatives to aporphine alkaloids via <i>ortho</i>-quinol intermediates. The two-step flow process involves an initial oxidative dearomatization of reticuline derivatives to using hypervalent iodine(III) reagents, followed by a TMSOTf-mediated electrophilic cyclization. The high sensitivity of <i>ortho</i>-quinol compounds is mitigated by the mild experimental conditions and fast reaction rates offered by flow reactors. A preliminary structure–reactivity relationship suggests that both steps of the process are favored with strongly electron-rich substrates, similar to what is observed in nature.</p>","PeriodicalId":630,"journal":{"name":"Journal of Flow Chemistry","volume":"13 3","pages":"257 - 265"},"PeriodicalIF":2.7,"publicationDate":"2023-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4492752","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organolithium compounds have been used successfully in flow chemistry since the recent past. Most of the studies dealt with the use in halogen-lithium exchanges. So far, however, there has been a lack of use in substitution reactions. The use of flow microreactors makes the highly reactive organolithium compounds more controllable and thus creates new synthetic possibilities.
{"title":"Selective monosubstitution on a trichlorosilane with highly reactive organolithium compounds in a microflow reactor","authors":"Moritz Achternbosch, Lukas Zibula, Annika Schmidt, Waldemar Krieger, Norbert Kockmann, Carsten Strohmann","doi":"10.1007/s41981-022-00254-w","DOIUrl":"10.1007/s41981-022-00254-w","url":null,"abstract":"<div><p>Organolithium compounds have been used successfully in flow chemistry since the recent past. Most of the studies dealt with the use in halogen-lithium exchanges. So far, however, there has been a lack of use in substitution reactions. The use of flow microreactors makes the highly reactive organolithium compounds more controllable and thus creates new synthetic possibilities.</p></div>","PeriodicalId":630,"journal":{"name":"Journal of Flow Chemistry","volume":"13 1","pages":"9 - 12"},"PeriodicalIF":2.7,"publicationDate":"2022-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s41981-022-00254-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5034487","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-12-12DOI: 10.1007/s41981-022-00251-z
Timothy Aljoscha Frede, Nick Nikbin, Norbert Kockmann
Continuous flow calorimeters are a promising tool in process development and safety engineering, especially for flow chemistry applications to characterize the heat release and kinetic parameters of rapid chemical reactions. In this study, the digital accompaniment of an isoperibolic flow calorimeter for characterization of exothermic reactions is presented. To support experimental planning and evaluation, computational fluid dynamic simulations are carried out for single-phase flow in the microreactor. The residence time distribution is obtained and used for estimation of conversion and temperature profiles along the microreactor channel. This leads to an integration of CFD simulations into the calorimeter’s software-guided workflow reducing the experimental effort regarding the determination of thermokinetic data. The approach is tested for a highly exothermic test reaction, which provides further hints for future investigations.
{"title":"Reactor performance estimation in microscale flow calorimeter for rapid characterization of exothermic reactions","authors":"Timothy Aljoscha Frede, Nick Nikbin, Norbert Kockmann","doi":"10.1007/s41981-022-00251-z","DOIUrl":"10.1007/s41981-022-00251-z","url":null,"abstract":"<p>Continuous flow calorimeters are a promising tool in process development and safety engineering, especially for flow chemistry applications to characterize the heat release and kinetic parameters of rapid chemical reactions. In this study, the digital accompaniment of an isoperibolic flow calorimeter for characterization of exothermic reactions is presented. To support experimental planning and evaluation, computational fluid dynamic simulations are carried out for single-phase flow in the microreactor. The residence time distribution is obtained and used for estimation of conversion and temperature profiles along the microreactor channel. This leads to an integration of CFD simulations into the calorimeter’s software-guided workflow reducing the experimental effort regarding the determination of thermokinetic data. The approach is tested for a highly exothermic test reaction, which provides further hints for future investigations.</p>","PeriodicalId":630,"journal":{"name":"Journal of Flow Chemistry","volume":"13 1","pages":"31 - 44"},"PeriodicalIF":2.7,"publicationDate":"2022-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s41981-022-00251-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4485662","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The synthesis of dithiocarbamates derivatives is important for their practical utilization as pharmaceuticals and for other purposes. Herein, we demonstrated the TfOH-catalyzed synthesis of dithiocarbamates via three-component reaction of α-diazoesters in good yields under continuous flow conditions. The reaction exhibits a wide substrate scope of diazo compounds and high functional group tolerance. This study provides a safe and mild protocol to form dithiocarbamates that complements TfOH-catalyzed S-H insertion reaction of diazo compounds and continuous flow synthesis strategies.
{"title":"TfOH-catalyzed three-component synthesis of Dithiocarbamates from α-Diazoesters under continuous flow conditions","authors":"Rui Wang, Hangli He, Qiongjiao Yan, Wei Wang, Haifeng Wang, Fener Chen","doi":"10.1007/s41981-022-00249-7","DOIUrl":"10.1007/s41981-022-00249-7","url":null,"abstract":"<div><p>The synthesis of dithiocarbamates derivatives is important for their practical utilization as pharmaceuticals and for other purposes. Herein, we demonstrated the TfOH-catalyzed synthesis of dithiocarbamates via three-component reaction of <i>α</i>-diazoesters in good yields under continuous flow conditions. The reaction exhibits a wide substrate scope of diazo compounds and high functional group tolerance. This study provides a safe and mild protocol to form dithiocarbamates that complements TfOH-catalyzed S-H insertion reaction of diazo compounds and continuous flow synthesis strategies.</p></div>","PeriodicalId":630,"journal":{"name":"Journal of Flow Chemistry","volume":"13 1","pages":"1 - 8"},"PeriodicalIF":2.7,"publicationDate":"2022-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4489614","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-12-05DOI: 10.1007/s41981-022-00248-8
Erin E. Brown
Phenols are vital building blocks for manufactured goods, agrochemicals, and medicine. As the demand to circumvent fossil fuels intensifies, so does the need to establish alternate sources of chemical feedstock, with many researchers looking to biomass. Lignin, a complex biopolymer found in plants, represents a relatively untapped renewable source of phenolic compounds. Examples of aromatic compounds derived from lignin include phenol, guaiacol (2-methoxyphenol), and catechol (2-hydroxyphenol). The development of new technologies and chemistry to upgrade or modify these compounds is crucial to realizing the potential of biomass as chemical feedstock. Over the last two decades, continuous flow technology has become an established tool for chemists to expand the capabilities of reaction control and to provide a means to probe novel reactions that might otherwise be difficult to study or accomplish via conventional means. Flow also imparts many advantages, such as superior mixing capabilities for gas/liquid reactions, increased efficiency for photochemical transformations, and improved scalability. This mini review will highlight research efforts reported in the last half-decade (since 2016) toward upgrading lignin-derived phenolic substrates using continuous flow technology. Recent developments focus on reactions requiring oxygenation, oxidation, hydrogenation, and deoxygenation to name a few.