The Chapman rearrangement in a continuous-flow microreactor

Fang, Jingjie; Ke, Miaolin; Huang, Guanxin; Tao, Yuan; Cheng, Dajun; Chen, Fen‐Er

doi:10.1039/c9ra01347d

Cited by 10 publications

(6 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, it should be noted that batch kinetics models cannot always be extrapolated to predict kinetics in flow due to specific mixing and/or dispersion effect attributes. In this case, a specific model constructed on kinetics data generated in flow must be followed …”

Section: How? Methodologies To Access Superheated Flow Chemistrymentioning

confidence: 99%

New Opportunities for Organic Synthesis with Superheated Flow Chemistry

Bianchi,

Monbaliu

2024

Acc. Chem. Res.

View full text Add to dashboard Cite

Metrics & MoreArticle Recommendations CONSPECTUS: Flow chemistry has brought a fresh breeze with great promises for chemical manufacturing, yet critical deterrents persist. To remain economically viable at production scales, flow processes demand quick reactions, which are actually not that common. Superheated flow technology stands out as a promising alternative poised to confront modern chemistry challenges. While continuous micro-and mesofluidic reactors offer uniform heating and rapid cooling across different scales, operating above solvent boiling points (i.e., operating under superheated conditions) significantly enhances reaction rates. Despite the energy costs associated with high temperatures, superheated flow chemistry aligns with sustainability goals by improving productivity (process intensification), offering solvent flexibility, and enhancing safety. However, navigating the unconventional chemical space of superheated flow chemistry can be cumbersome, particularly for neophytes. Expanding the temperature/pressure process window beyond the conventional boiling point under the atmospheric pressure limit vastly increases the optimization space. When associated with conventional trial-and-error approaches, this can become exceedingly wasteful, resource-intensive, and discouraging. Over the years, flow chemists have developed various tools to mitigate these challenges, with an increased reliance on statistical models, artificial intelligence, and experimental (kinetics, preliminary test reactions under microwave irradiation) or theoretical (quantum mechanics) a priori knowledge. Yet, the rationale for using superheated conditions has been slow to emerge, despite the growing emphasis on predictive methodologies. To fill this gap, this Account provides a concise yet comprehensive overview of superheated flow chemistry. Key concepts are illustrated with examples from our laboratory's research, as well as other relevant examples from the literature. These examples have been thoroughly studied to answer the main questions Why? At what cost? How? For what? The answers we provide will encourage educated and widespread adoption. The discussion begins with a demonstration of the various advantages arising from superheated flow chemistry. Different reactor alternatives suitable for high temperatures and pressures are then presented. Next, a clear workflow toward strategic adoption of superheated conditions is resorted either using Design of Experiments (DoE), microwave test chemistry, kinetics data, or Quantum Mechanics (QM). We provide rationalization for chemistries that are well suited for superheated conditions (e.g., additions to carbonyl functions, aromatic substitutions, as well as C−Y [Y = N, O, S, C, Br, Cl] heterolytic cleavages). Lastly, we bring the reader to a rational decision analysis toward superheated flow conditions. We believe this Account will become a reference guide for exploring extended chemical spaces, accelerating organic synthesis, and advancing molecular sciences.

show abstract

Section: How? Methodologies To Access Superheated Flow Chemistrymentioning

confidence: 99%

New Opportunities for Organic Synthesis with Superheated Flow Chemistry

Bianchi,

Monbaliu

2024

Acc. Chem. Res.

View full text Add to dashboard Cite

show abstract

“…[22][23][24][25][26][27][28][29][30][31][32][33][34][35] Moreover, named reactions including Ritter reaction, Beckmann rearrangement, Chapman rearrangement, Schmidt reaction, Passerini reaction, and Ugi-type multicomponent reactions for amide synthesis have also been well explored in the literature for amide synthesis. [36][37][38][39][40][41][42][43] Based on the above discussion, it is apparent that direct access to amides with minimization of waste by-products is highly desirable from an economic and ecological point of view. In the past few decades, impressive research efforts have been devoted to synthetic methods able to surpass the aforementioned limitations.…”

Section: Introductionmentioning

confidence: 99%

“…22–35 Moreover, named reactions including Ritter reaction, Beckmann rearrangement, Chapman rearrangement, Schmidt reaction, Passerini reaction, and Ugi-type multicomponent reactions for amide synthesis have also been well explored in the literature for amide synthesis. 36–43 Based on the above discussion, it is apparent that direct access to amides with minimization of waste by-products is highly desirable from an economic and ecological point of view.…”

Section: Introductionmentioning

confidence: 99%

Green and sustainable visible light-mediated formation of amide bonds: an emerging niche in organic chemistry

Singh

Sharma

2022

New J. Chem.

View full text Add to dashboard Cite

show abstract

“…Recently, continuous-flow technology has been widely used in enzymatic reactions, and the combination of biological catalytic technology and flow chemistry opens influential novel process windows [31][32][33][34][35]. With the advantages of high specific surface area, good heat transfer performance and efficient mixing, continuous-flow reactors can increase the reaction efficiency and selectivity [36][37][38].…”

Section: Introductionmentioning

confidence: 99%

Ring-Opening of Epoxides with Amines for Synthesis of β-Amino Alcohols in a Continuous-Flow Biocatalysis System

Xue

Yang

et al. 2020

Catalysts

View full text Add to dashboard Cite

An efficient method for the preparation of β-amino alcohols catalyzed by lipase TL IM from Thermomyces lanuginosus in a continuous-flow reactor was developed. The eco-friendly biocatalyst combined with continuous-flow reaction technology displayed high efficiency in the synthesis of β-amino alcohols. The benign reaction conditions (35 °C) and short residence time (20 min), together with the use of low cost and readily available starting materials, make this synthetic approach a promising alternative to current β-amino alcohol synthesis.

show abstract

The Chapman rearrangement in a continuous-flow microreactor

Abstract: A microreactor-based continuous flow method was developed for the high temperature Chapman rearrangement, which was found to be efficient, controllable, safe and scalable.

Cited by 10 publications

References 35 publications

New Opportunities for Organic Synthesis with Superheated Flow Chemistry

New Opportunities for Organic Synthesis with Superheated Flow Chemistry

Green and sustainable visible light-mediated formation of amide bonds: an emerging niche in organic chemistry

Ring-Opening of Epoxides with Amines for Synthesis of β-Amino Alcohols in a Continuous-Flow Biocatalysis System

Contact Info

Product

Resources

About