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Green Foundation box

09 Sep 2024
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The Green Foundation box

From the beginning of December 2024, all submitted manuscripts to Green Chemistry must include a Green Foundation box. This box should contain three numbered points answering three specific questions based on the article type (140 words maximum). This box will be seen by the editor and reviewers and will help them ascertain the green advance that the work presents. If the manuscript is accepted this box will also be published. Manuscripts cannot be considered by the editor or reviewed without this box. More information can be found in this Editorial

The questions to be answered are:

Primary research: Communications and Full Papers
1. How does your work advance the field of green chemistry?
2. Please can you describe your specific green chemistry achievement, either quantitatively or qualitatively?
3. How could your work be made greener and be elevated by further research?

 Secondary research: Critical reviews, Tutorial reviews, and Perspectives
1. What advances in green chemistry have been discussed?
2. What makes the area of study of significant wider interest?
3. What will the future of this field hold, and how will the insight in your review help shape green chemistry science?

Examples

The Editorial Office, in collaboration with past and present Editorial Board Members, have put together a list examples based on recently published articles.

Click below to read the examples.

Article type: Communications
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Electrochemical-induced benzyl C–H amination towards the synthesis of isoindolinones via aroyloxy radical-mediated C–H activation
M. Yu, Y. Gao, L. Zhang, Y. Zhang, Y. Zhang, H. Yi, Z. Huang and A. Lei
Green Chem., 2022, 24, 1445-1450. DOI: 10.1039/D1GC04676D

Green foundation
  1. We report a cost-effective, safe, and sustainable electrochemical strategy to effectively and selectively realize benzyl C–H amination via aroyloxy radical-mediated C–H activation. With this strategy, we are able to rapidly synthesize a set of valuable isoindolinones by using easily available o-alkyl benzoic acids and nitriles as starting materials under mild conditions without the use of transition metal catalysts and external oxidants.
  2. The synthetic value of this method is also illustrated by post-derivatizations to newly accessible scaffolds, thus paving the way towards versatile molecules of interest with potential pharmaceutical applications. We present a “green” concept starting with simple starting materials and through sustainable reaction conditions we provide an effective synthetic pathway to a series of pharmaceutically relevant isoindolinones.
  3. It will be beneficial for organic chemists to access pharmaceuticals and natural products involving lactam skeletons, therefore, making contributions to the new drug development.

A highly active, thermally robust iron(iii)/potassium(i) heterodinuclear catalyst for bio-derived epoxide/anhydride ring-opening copolymerizations
W. T. Diment, G. Rosetto, N. Ezaz-Nikpay, R. W. F. Kerr and C. K. Williams
Green Chem., 2023, 25, 2262-2267. DOI:10.1039/D2GC04580J

Green foundation
  1. We investigate the synthesis of degradable polyesters from sustainable monomers mediated by an earth abundant metals, iron and potassium.
  2. The catalyst showed field-leading activity and selectivity for highly challenging, renewable monomers. It efficiently produced a series of amorphous, high Tg (>100 °C) polyesters, which carry significant potential as degradable thermoplastics, engineering polymers, resins and vitrimers.
  3. The Fe(iii)/K(i) combination should be tested with other ancillary ligands and as catalysts targeted for other sustainable polymerizations, e.g. carbon dioxide/epoxide ROCOP or lactide, lactone or cyclic carbonate ring-opening polymerizations which may benefit from heterodinuclear synergy.

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Article type: Full papers
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Assessing the environmental benefit of palladium-based single-atom heterogeneous catalysts for Sonogashira coupling
D. Faust Akl, D. Poier, S. C. D’Angelo, T. P. Araújo, V. Tulus, O. V. Safonova, S. Mitchell, R. Marti, G. Guillén-Gosálbez and J. Pérez-Ramírez
Green Chem., 2022, 24, 6879-6888. DOI: 10.1039/D2GC01853E

Green foundation
  1. This study quantitatively assesses through life-cycle analysis (LCA) possible environmental benefits of replacing soluble palladium organometallic complexes with single-atom heterogeneous catalysts in cross-coupling reactions, exemplified for the Sonogashira reaction.
  2. Reusing the heterogeneous catalyst once, assuming its stability and full metal retention, can already deliver advantages in various impact categories over the conventional homogeneous systems, with the potential for orders-of-magnitude improvements. The LCA results provide criteria for implementing solid, reusable catalysts in sustainable organic transformations.
  3. In future work, the presented LCA framework may inform catalyst design and help streamline research efforts toward more sustainable catalytic materials.

High performance, but low cost and environmental impact? Integrated techno-economic and life cycle assessment of polyoxazolidinone as a novel high-performance polymer
M. Bachmann, A. Marxen, R. Schomäcker and A. Bardow
Green Chem., 2022, 24, 9143-9156. DOI:10.1039/D2GC02400D

Green foundation
  1. This work assesses the economic and environmental potential of polyoxazolidinones (POX) as high-performance thermoplastics.
  2. A combined techno-economic and life-cycle assessment shows that POX reduce the carbon footprint of high-performance thermoplastics at competitive costs even for fossil-based production. Employing biomass could further reduce the carbon footprint but would introduce environmental trade-offs such increasing freshwater eutrophication.
  3. POX are identified as promising as high-performance thermoplastics, but the assumed material performance needs to be confirmed experimentally and environmental trade-offs considered in detail before large-scale implementation.

Early-stage impact assessment tool (ESTIMATe) for the life cycle assessment of CO2-based chemicals
H. Minten, B. D. Vandegehuchte, B. Jaumard, R. Meys, C. Reinert and A. Bardow
Green Chem., 2024, 26, 8728-8743. DOI:10.1039/D4GC00964A

Green foundation
  1. This work introduces a software tool allowing non-experts to perform early-stage life-cycle assessment for CO2 conversion processes.
  2. The open-source Excel tool ESTIMATe is provided that automates and streamlines life-cycle assessment of carbon capture and utilization processes. LCA assumptions are automated and estimation tools are provided to fill data gaps. Thereby, ESTIMATe makes environment assessments accessible to non-experts even at early-stages of development.
  3. Deployment of the ESTIMATe tool will hopefully improve early-stage decision making and also help to refine the tool itself. Future developments are to expand the scope beyond CO2 conversion.

Introducing the use of a recyclable solid electrolyte for waste minimization in electrosynthesis: preparation of 2-arylbenzoxazoles under flow conditions
F. Ferlin, F. Valentini, F. Campana and L. Vaccaro
Green Chem., 2024, 26, 6625-6633. DOI:10.1039/D4GC00930D

Green foundation
  1. The work introduces the use of solid electrolyte into organic electrosynthesis, and it proves that with this approach is possible to significantly reduce the waste associated to the use of stochiometric classic homogeneous electrolyte generally containing halides
  2. Calculation of the green metrics (E-factors, RME, MRP) for the newly defined procedure and several literature examples, allow to quantify the specific achievement. E-factor has been reduced of ca. 82-99%. Mass of the electrolyte generally constitutes 25–68% of the entire E-kernel and in our case, we could obtain a very low value of 0.12%.
  3. Future research will be dedicated to expanding the utilization of solid electrolyte in different electroassisted processes using with safe recoverable reaction media.

Valorisation of phenols to coumarins through one-pot palladium-catalysed double C–H functionalizations
G. Brufani, F. Valentini, F. Sabatelli, B. Di Erasmo, A. M. Afanasenko, C.-J. Li and L. Vaccaro
Green Chem., 2022, 24, 9094-9100. DOI:10.1039/D2GC03579K

Green foundation
  1. The use of a novel synthetic strategy based on the Pd/C catalysed C−H functionalization of substituted phenols has allowed the direct synthesis of prenylated coumarins. The multistep protocols for the synthesis of osthole-like derivatives, which frequently use toxic reagents and non-recyclable catalysts, could be replaced using our one-pot procedure, which has proven to be efficient in the synthesis of biologically active products.
  2. Our newly procedures for the synthesis of osthole derivates showed significant improvement in terms of atom economy, from 32% to 81%. For direct comarin synthesis, the waste was reduced up to 56% and the efficient recovery and reuse of heterogeneous catalytic system has allowed a TON value of 41 (over 5 consecutive runs) which is greater than the value obtained for analogous homogeneous systems (6.2–32.3).
  3. Further work on the kinetics and the mechanism would aid in future research particularly for other derivatives

Aerobic waste-minimized Pd-catalysed C–H alkenylation in GVL using a tube-in-tube heterogeneous flow reactor
F. Ferlin, I. Anastasiou, L. Carpisassi and L. Vaccaro.
Green Chem., 2021, 23, 6576-6582. DOI:10.1039/D1GC01870A

Green foundation
  1. We utilize an efficient flow reactor system for the Fujiwara–Moritani C–H alkenylation reaction of biomass-derived γ-valerolactone. The protocol features very limited metal leaching, high stability of the catalyst, and applicability to a range of substituted acetanilides and N-methoxybenzamides and others.
  2. By using the flow reactor system, the external oxidant could be minimised, which also reduced leaching of the palladium catalyst (from ca. 4 ppm to 0.2–0.02 ppm). The use of biomass derived GVL as the reaction medium also reduced metal leaching by almost an order of magnitude to the next best solvent. By comparing to protocols in the literature, the E-factor value of our newly defined protocol is 80->99% lower and the reaction mass efficiency and materials recovery parameter are noticeably improved.
  3. When scaling up, an efficient recovery process for the leached palladium would be critical for a sustainable system.

Non-noble metal heterogeneous catalysts for hydrogen-driven deoxydehydration of vicinal diol compounds
J. Gan, Y. Nakagawa, M. Yabushita and K. Tomishige.
Green Chem., 2024, 26, 8267-8281. DOI:10.1039/D4GC02006E

Green foundation
  1. From the viewpoint of carbon neutrality and carbon recycling, the synthesis of biomass to valuable chemicals using greener catalysts is increasingly important. The present work shows the development of non-noble metal catalysts for deoxydehydration (DODH).
  2. Rather than use noble metal catalysts like Re or Au, we show the development and activity of a range of non-noble metal catalysts for the DODH reaction of 1,4-anhydroerythritol, a typical biomass-derived platform molecule, and demonstrate comparable yields of the target product. The new catalyst could be reused after calcination without loss of activity.
  3. An environmental impact assessment of the catalyst preparation and the final process could help guide the next steps.

Accessing secondary amine containing fine chemicals and polymers with an earth-abundant hydroaminoalkylation catalyst
M. Manßen, S. S. Scott, D. Deng, C. H. M. Zheng and L. L. Schafer.
Green Chem., 2023, 25, 2629-2639. DOI:10.1039/D3GC00011G

Green foundation
  1. We present a titanium-catalysed hydroaminoalkylation process, as a greener alternative to the industrially accepted hydroaminomethylation transformation, which relies on rhodium hydroformylation catalysts.
  2. Our Ti(NMe2)4/ligand system showed activity for an increased diversity of substrates, excellent regioselectivity, simple catalyst design, and quantifiable improvement on standard environmental assessment metrics. Compared to the best-in-class tantalum hydroaminoalkylation catalyst, our catalyst based on Ti(NMe2)4/ligand was shown by LCA to be less impactful in five out of nine categories for amine terminated polypropylene synthesis.
  3. This Ti(NMe2)4/ligand system could also be used for challenging postpolymerisation of macromolecular substrates, where this catalyst and process would offer a greener alternative.

Ultrasonic-assisted oxidation of cellulose to oxalic acid over gold nanoparticles supported on iron-oxide
P. N. Amaniampong, Q. T. Trinh, T. Bahry, J. Zhang and F. Jérôme.
Green Chem., 2022, 24, 4800-4811. DOI:10.1039/D2GC00433J

Green foundation
  1. The global market for oxalic acid was around 1340 thousand tons in 2022. Here we present a greener alternative to the harsh conditions regularly required in industry to overcome the recalcitrance of cellulose in chemical processing.
  2. We demonstrate that low frequency ultrasound induces the fragmentation of cellulose particles to facilitate the otherwise highly challenging, base-free oxidation of cellulose to oxalic acid. We show that ultrasonic conditions lead to partial fragmentation of cellulose particles, making it more reactive with the catalyst.
  3. Full elucidation and greater understanding of the role of ultrasonic conditions on the reaction mechanism is required.

Development of a solvent sustainability guide for the paints and coatings industry
L. Pilon, D. Day, H. Maslen, O. P. J. Stevens, N. Carslaw, D. R. Shaw and H. F. Sneddon.
Green Chem., 2024, Advance Article. DOI:10.1039/D4GC01962H

Green foundation
  1. The paints and coatings industry has increasingly been moving towards lower emissions and the nature of the solvents considered in future is anticipated to come under increasing scrutiny. A solvent sustainability guide is offered for the paints and coatings industry, considering solvents likely of interest in this sector, and considering criteria relevant to these applications.
  2. A range of solvents relevant to this sector were compared. While instances where like-for-like drop-in replacements can be identified are expected to be few, the guide allows ready identification of a range of greener or more sustainable solvents as possible start points for further formulation research.
  3. New solvent data continues to be collected, and regulations evolve, therefore, it is essential to only to use this guide in conjunction with reliable sources to obtain the most current information.

Selectivity switch by phase switch – the key to a high-yield furfural process
L. Ricciardi, W. Verboom, J.-P. Lange and J .Huskens
Green Chem., 2021, 23, 8079-8088.  DOI:10.1039/D1GC01752G

Green foundation
  1. Furfural is a versatile intermediate for biofuels and bio-based chemicals. We present a greener alternative to the industrial process that converts xylose-rich hydrolysate to furfural with higher yield.
  2. High xylose-to-furfural yield at and above approx. 90 mol%, becomes feasible with a variety of solvent combinations and phenylboronic acid concentrations. A conceptual process design for scaled-up furfural production is presented, where the produced furfural could be recovered from the system with modest losses of the solvents in the waste streams, and thus minimizing waste and maximizing recyclability.
  3. Additional research is needed to (1) finetune the selection of solvent and boronic acid to further minimize losses and toxicity/environmental risks, (2) validate the process concept and (3) deliver the information needed for designing the major pieces of equipment.

 

Article type: Perspectives
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Energy crisis in Europe enhances the sustainability of green chemicals
A. Nabera, I.-R. Istrate, A. José Martín, J. Pérez-Ramírez and G. Guillén-Gosálbez.
Green Chem., 2023, 25, 6603-6611. DOI:10.1039/D3GC01053H

Green foundation
  1. Global production of ammonia and methanol are key elements of the chemical industry. Recent increases in energy prices in Europe have created a recent scenario where renewable options for both ammonia and methanol had the potential to outperform their fossil counterparts for six months (as of December 2021).
  2. If the European chemical industry can establish cost-competitive production routes of green ammonia and methanol, overcoming the primary obstacle to their implementation, then they have the opportunity to lead the transition and global movement towards environmentally responsible practices, while simultaneously reaping significant economic benefits in the long run.
  3. Global concerns regarding the environment and the price of sustainability means that identifying cost competitive low-carbon technologies are of special interest. With a coordinated effort from academia, industry, and policymakers, Europe can lead the grand transition towards more sustainable practices in the chemical industry.

Recent advances in the heterogeneous photochemical synthesis of C–N bonds
J. J. Wang, Y. Liu, X. Zong, A. Lei and Z. Sun.
Green Chem., 2023, 25, 5010-5023. DOI:10.1039/D3GC00931A

Green foundation
  1. Classical activation of C-N bonds with chemical processes can be made greener through photoactivation and the utilization of sunlight. We discuss the structure, characteristics, and reactivity of different types of heterogeneous photocatalysts for C–N coupling reactions.
  2. The synthesis and development of heterogeneous photocatalysts has progressed faster than testing for C-X activation. Herin, we summarize the most recent developments in photocatalysts, how they apply to C-X activation using C-N as an example, and then how reactions may be scaled up with a flow reactor.
  3. Many C-X activation reactions remain unresearched and providing greener alternatives to chemical reactions through the application of sunlight remains a high challenge. Scaling up photoactivated reactions to become industrially relevant would have a great impact.
Article type: Critical Reviews
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Lignin for energy applications – state of the art, life cycle, technoeconomic analysis and future trends
A. Beaucamp, M. Muddasar, I. Saana Amiinu, M. Moraes Leite, M. Culebras, K. Latha, M. C. Gutiérrez, D. Rodriguez-Padron, F. del Monte, T. Kennedy, K. M. Ryan, R. Luque, M.-M. Titirici and Maurice N. Collins.
Green Chem., 2022, 24, 1445-1450. DOI: 10.1039/D2GC02724K

Green foundation
  1. Lignin is finding application in a remarkable array of materials for different energy applications from electrodes through to batteries. Here we assess the environmental impact of recent discoveries and the viability of future outcomes.
  2. Lignin is a by-product of several global industries. Research into its efficient processing and use is of wide interest, especially for certain use cases where more expensive or less green materials can be replaced.
  3. The emergence of economically viable biorefineries is a welcome step for the use of lignin for energy applications. However, for example, the depolymerisation processes are yet to be fully upscaled. For batteries, improvements in performance of lignin-based electrodes in full cell batteries should be the ultimate ambition.

Classic vs. C–H functionalization strategies in the synthesis of APIs: a sustainability comparison
F. Ferlin, G. Brufani, G. Rossinia and L. Vaccaro.
Green Chem., 2023, 25, 7916-7933. DOI:10.1039/D3GC02516K

Green foundation
  1. The research and discovery of efficient routes of synthesis for active pharmaceutical ingredients is an extraordinary challenge. We discuss and compare the relative sustainability and greenness of a range of functionalization strategies.
  2. There are significant and important demands to look at the environmental and safety impact of C–H functionalization methodologies from academia to industry. The adoption of green technologies and strategies for C–H functionalization adds to the transition to sustainable methodologies.
  3. Development of techno-economic studies on this subject would provide further opportunities for research and pave the way for the development of greener chemical methodologies.

Safe and sustainable chemicals and materials: a review of sustainability assessment frameworks
J. C. Caldeira, E. Abbate, C. Moretti, L. Mancinia and S. Sala.
Green Chem., 2024, 26, 7456-7477. DOI:10.1039/D3GC04598F

Green foundation
  1. We discuss how sustainability has been implemented in frameworks that are used to identify criteria for safe and sustainable by design chemicals and materials – particularly frameworks that consider more than one sustainability dimension (e.g., safety, environmental, social, and economic).
  2. This broad scope assessment of a range of frameworks from over 155 sources from academia, industry and government, allows for systematic comparison. By following these frameworks and studying the relative criteria, viable or alternative chemicals and materials can be screened before commercialization to avoid regrettable substitutions.
  3. Future studies to produce a comprehensive set of indicators for examining the sustainability of a chemical within proposals of frameworks from academia, governments, NGOs, or industry, are needed and also a well-defined method for assessing circularity.

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Article type: Tutorial Reviews
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Advances in catalytic dehydrogenation of ethanol to acetaldehyde
J. Pang, M. Yin, Pengfei Wu, X. Li, H. Li, M. Zheng and T. Zhang.
Green Chem., 2021, 23, 7902-7916. DOI: 10.1039/D1GC02799A

Green foundation
  1. We discuss greener methods to partially or totally replace fossil-based acetaldehyde. Owing to the wide range of applications of acetaldehyde, the catalytic conversion of ethanol to acetaldehyde has been extensively studied.
  2. Acetaldehyde is an important commodity with an annual production of over 106 tons. It is a key reagent or solvent for the production of a variety of industrial chemicals, such as peracetic acid, pentaerythritol and pyridine-based products. After years of study, the dehydrogenation of ethanol to acetaldehyde has developed to the point that it is a promising way to replace the fossil ethylene method, which uses Ag catalysts at a large scale even though these catalysts still face deactivation and regeneration issues.
  3. Although some interesting catalysts have been developed for oxidative and non-oxidative ethanol dehydrogenations, there remains significant work before these processes are commercially viable, especially over non-noble metal catalysts.

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