Sequential Continuous Flow Processes for the Oxidation of Amines and Azides by using HOF⋅MeCN

McPake, Christopher B.; Murray, Christopher B.; Sandford, Graham

doi:10.1002/cssc.201100423

Cited by 20 publications

(22 citation statements)

References 38 publications

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“…The examples in Figure 15C (Brooke et al, 1961;McPake et al, 2012), Figure 15D (Chadwick et al, 2010;Pieri et al, 2014;Jong and Bradley, 2015) and Figure 15E (Jirkovsky, 1974;Pathak et al, 2014;OBrien and Cooper, 2016) show how the model correctly preserves the components for the flow-benefitting cases, while it adjusts the components for the non-benefitting cases.…”

Section: Proposition Of Alternative Reaction Components Approachmentioning

confidence: 98%

Artificial Intelligence for Computer-Aided Synthesis In Flow: Analysis and Selection of Reaction Components

et al. 2020

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Computer-aided synthesis has received much attention in recent years. It is a challenging topic in itself, due to the high dimensionality of chemical and reaction space. It becomes even more challenging when the aim is to suggest syntheses that can be performed in continuous flow. Though continuous flow offers many potential benefits, not all reactions are suited to be operated continuously. In this work, three machine learning models have been developed to provide an assessment of whether a given reaction may benefit from continuous operation, what the likelihood of success in continuous flow is for a certain set of reaction components (i.e., reactants, reagents, solvents, catalysts, and products) and, if the likelihood of success is low, which alternative reaction components can be considered. The first model uses an abstract version of a reaction template, obtained via gaussian mixture modeling, to quantify its relative increase in publishing frequency in continuous flow, without relying on potentially ambiguously defined reaction templates. The second model is an artificial neural network that categorizes feasible and infeasible reaction components with a 75% success rate. A set of reaction components is considered to be feasible if there is an explicit reference to it being used in continuous synthesis in the database; all other reaction components are considered infeasible. While several cases that are "infeasible" by this definition, are classified as feasible by the neural network, further analysis shows that for many of these cases, it is at least plausible that they are in fact feasible-they simply have not been tested to (dis)prove this. The final model suggests alternative continuous flow components with a top-1 accuracy of 95%. Combined, they offer a black-box evaluation of whether a reaction and a set of reaction components can be considered promising for continuous syntheses.

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Section: Proposition Of Alternative Reaction Components Approachmentioning

confidence: 98%

Artificial Intelligence for Computer-Aided Synthesis In Flow: Analysis and Selection of Reaction Components

et al. 2020

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“…The relatively poor stability of the HOF•MeCN complex (half-life at room temperature of approximately 4 h) and the undesired transformations often occurring in highly concentrated oxidising media represent the main drawbacks of HOF•MeCN-based procedures. McPake et al aimed to address these issues by developing a sequential continuous flow process for the oxidation of amines [81]. Fluorine and aqueous acetonitrile are reacted to generate HOF•MeCN, which is immediately treated with the amine in a single, sequential, twostep flow process.…”

Section: Oxidations With Other Oxidising Agentsmentioning

confidence: 99%

Synthesis of Nitroarenes by Oxidation of Aryl Amines

Capperucci

Tanini

2022

Chemistry

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Nitro compounds are an important class of organic molecules with broad application in organic synthesis, medicinal chemistry, and materials science. Among the variety of methodologies available for their synthesis, the direct oxidation of primary amines represents an attractive alternative route. Efforts towards the development of oxidative procedures for the synthesis of nitro derivatives have spanned over the past decades, leading to a wide variety of protocols for the selective oxidative conversion of amines to nitro derivatives. Methods for the synthesis of nitroarenes via oxidation of aryl amines, with particular emphasis on recent advances in the field, are summarised in this review.

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“…Therefore, the use of HOF⋅MeCN in large‐scale processes can be solved by the flow technique. In this contest, Sandford et al . demonstrated the convenience of appling this technology to the oxidation of primary amines with the HOF⋅CH 3 CN complex.…”

Section: Oxidation Of Nitrogen Derivativesmentioning

confidence: 99%

“…As for the oxidation of amines with HOF⋅CH 3 CN in a flow process, azides have been converted into nitroalkanes in flow by using the equipment of Figure . Following this process (Scheme ), nitroalkanes 14 are obtained in nearly quantitative yields without any purification step.…”

Section: Oxidation Of Nitrogen Derivativesmentioning

confidence: 99%

Synthetic Procedures for the Preparation of Nitroalkanes

Ballini

Palmieri

2018

Adv Synth Catal

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Nitroalkanes, mainly the primary ones, are the keys tarting materials for the synthesis of al arge variety of important targets.H owever, in spite of their strategic synthetic importance,e very single type of nitroalkane ande very single procedure are relegated to individual contributions.T hus,t his review represents the first exhaustive collectiono f procedures for their synthesisa nd,c onsequently,i t can be considereda savery important tool for a growing use of nitroalkanes as key synthetic building blocks. Scheme 18. b-Keto-w-nitrotrimethylsilanes 60. Scheme19. Preparation of 61 b-nitrocycloalkanols. Scheme20. Synthesis of ketonitroalkanes 62. Scheme 34. Conversion of b-nitrostyrenes into a-nitro acetophenones. Scheme 35. Conversion of olefins into a-nitro ketones. Scheme36. Synthesis of b-nitro carbonyl compounds. Scheme37. Protection of 3-nitropropanal.

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Sequential Continuous Flow Processes for the Oxidation of Amines and Azides by using HOF⋅MeCN

Cited by 20 publications

References 38 publications

Artificial Intelligence for Computer-Aided Synthesis In Flow: Analysis and Selection of Reaction Components

Artificial Intelligence for Computer-Aided Synthesis In Flow: Analysis and Selection of Reaction Components

Synthesis of Nitroarenes by Oxidation of Aryl Amines

Synthetic Procedures for the Preparation of Nitroalkanes

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