Article
Energy & Fuels
Tirath Raj, K. Chandrasekhar, Rajesh Banu, Jeong-Jun Yoon, Gopalakrishnan Kumar, Sang-Hyoun Kim
Summary: The review comprehensively summarized recent updates and catalytic approaches for GVL production, as well as its applications in biomass deconstruction, and discussed advancements, challenges, and future perspectives in GVL-based biorefinery.
Article
Chemistry, Organic
Jie Zhang, Shao-Qing Shi, Wen-Juan Hao, Guo-Yun Dong, Shu-Jiang Tu, Bo Jiang
Summary: Tunable electrocatalytic annulation reactions of o-arylalkynylanilines have been established, leading to the green and divergent syntheses of skeletally diverse indoles by adjusting the electrolytes and solvents.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Andrew Jordan, Callum G. J. Hall, Lee R. Thorp, Helen F. Sneddon
Summary: Dipolar aprotic and ethereal solvents are widely used in organic chemistry but face restrictions due to environmental and safety concerns. The search for alternative solvents that are more sustainable and safer has gained attention, and successful replacement of less-preferable solvents has been achieved.
Article
Engineering, Chemical
Lorenz Fleitmann, Johanna Kleinekorte, Kai Leonhard, Andre Bardow
Summary: Sustainable solvents are crucial for chemical processes and Computer-Aided Molecular and Process Design (CAMPD) offers a tailored approach for their applications. This study proposes a framework integrating Life Cycle Assessment (LCA) of solvents from cradle-to-grave, highlighting the importance of cradle-to-grave LCA in solvent design for holistic environmental assessment.
CHEMICAL ENGINEERING SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Shalini Arora, Neeraj Gupta, Vasundhara Singh
Summary: In this study, valorization of hemicellulose isolated from lignocellulosic biomass to furfural was achieved through pH-controlled acid catalysis using choline-based Bronsted acidic and natural acidic deep eutectic solvents. The optimal deep eutectic solvents were found to be ChCl/p-TSA and ChCl/levulinic acid, yielding 85% furfural. The reported methodology offers advantages such as using bio-based green solvents, mild reaction conditions, and efficient scale-up of the reaction.
Article
Chemistry, Physical
Aditi Prabhune, Ranjan Dey
Summary: Deep Eutectic Solvents (DESs) have emerged as potential alternatives to conventional solvents in many industrial applications due to their safety, greenness, ease of preparation and wide range of applications.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
Article
Chemistry, Multidisciplinary
Giulia Martelli, Paolo Cantelmi, Alessandra Tolomelli, Dario Corbisiero, Alexia Mattellone, Antonio Ricci, Tommaso Fantoni, Walter Cabri, Federica Vacondio, Francesca Ferlenghi, Marco Mor, Lucia Ferrazzano
Summary: The investigation identified N-octyl pyrrolidone (NOP) as the best candidate for solid phase peptide synthesis (SPPS) as an alternative to N,N-dimethylformamide (DMF), with improved performances and high purity peptides. A mixture of NOP with 20% dimethyl carbonate (DMC) reduced solvent viscosity and enabled the use in automated solid-phase protocol, while achieving an outstanding reduction in process mass intensity (PMI) by 63-66%, representing a significant step forward in achieving green SPPS.
Article
Agricultural Engineering
Chung Loong Yiin, Kok Liang Yap, Andrian Zi En Ku, Bridgid Lai Fui Chin, Serene Sow Mun Lock, Kin Wai Cheah, Adrian Chun Minh Loy, Yi Herng Chan
Summary: Biomass wastes have great potential for renewable energy and value-added product synthesis. The key lies in developing pretreatment techniques to overcome barriers in lignocellulosic materials and find cheap, effective, environmentally friendly methods. The use of green solvents and the role of choline chloride (ChCl) in them are areas of interest and ongoing research.
BIORESOURCE TECHNOLOGY
(2021)
Review
Chemistry, Organic
Uttam Dhawa, Nikolaos Kaplaneris, Lutz Ackermann
Summary: Transition metal catalyzed C-H activation has become a powerful tool in molecular synthesis, with recent focus on achieving high levels of resource economy to improve sustainability and environmental friendliness in synthesis processes.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Agricultural Engineering
Jiao Li, Tao Li, Yang Wang, Zicheng Du, Yadan Luo, Chengrong Qin, Chen Liang, Caoxing Huang, Shuangquan Yao
Summary: The effect of a bio-based solvent coupled pretreatment system on the separation of poplar biomass components was investigated, showing that the method can effectively separate cellulose and inhibit the repolymerization of lignin.
INDUSTRIAL CROPS AND PRODUCTS
(2023)
Article
Biochemistry & Molecular Biology
Huiqi Jin, Haiqiang Shi, Wenchao Jia, Yanning Sun, Xueru Sheng, Yanzhu Guo, Haiming Li, Haidong Sun
Summary: A green solvent system was developed for the molecular weight-controllable fractionation of industrial alkali lignin. The fractionation process, achieved by adjusting the ratio of water, ethanol, and gamma-Valerolactone, resulted in six levels of lignin with stepwise controllable molecular weight. The fractionation was confirmed to be a physical process without altering the chemical structure of lignin. The fractionated lignin with higher molecular weight exhibited narrower polydispersity and the fractionated lignin with lower molecular weight had higher content of hydroxyl and carboxyl groups, which could enhance its chemical reactivity in downstream applications.
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
(2022)
Article
Chemistry, Multidisciplinary
Nerea Gonzalez-Gallardo, Beatriz Saavedra, Gabriela Guillena, Diego J. Ramon
Summary: Deep eutectic solvents (DESs) have been successfully utilized as a sustainable medium for the first time in a ruthenium-catalyzed C-H activation reaction, enabling efficient and direct activation of a wide range of aromatic substrates. The choice of catalyst and reaction conditions makes this method highly applicable and outperforms the current literature.
Article
Chemistry, Multidisciplinary
Joshua D. Tibbetts, Marc Hutchby, William B. Cunningham, Robert S. L. Chapman, Gabriele Kociok-Koehn, Matthew G. Davidson, Steven D. Bull
Summary: Scalable processes have been developed to convert beta-pinene into 4-isopropenylcyclohexanone, which is then used as a feedstock for the divergent synthesis of sustainable versions of paracetamol and ibuprofen. The use of bioderived 4-hydroxyacetophenone as a replacement feedstock for sustainable aromatic products is also discussed within a terpene biorefinery context.
Article
Chemistry, Multidisciplinary
Swadhapriya Bhukta, Rana Chatterjee, Rambabu Dandela
Summary: A metal-free and efficient method for the synthesis of 1,2-diketones through oxidative C(sp)-H functionalization of alkynes has been developed. The oxidative addition of a phenyl radical generated from aniline to terminal alkynes, aided by a composite of tert-butyl nitrite and ascorbic acid, leads to the formation of α-diketones. This one-pot strategy employs 2-methyltetrahydrofuran (2-MeTHF) as an alternative reaction medium for the oxidative diketonation. The method allows for the synthesis of symmetrical and unsymmetrical substituted 1,2-diketones using easily accessible reactants, and offers promising features such as environmentally benign reagents, greener and renewable solvents, a broad range of substrates, large-scale synthesis, lower E-factors, practical applications, radical pathways, and mild reaction conditions.
Article
Chemistry, Physical
Jose B. G. Filho, Regiane D. F. Rios, Carlos G. O. Bruziquesi, Daniele C. Ferreira, Henrique F. V. Victoria, Klaus Krambrock, Marcio C. Pereira, Luiz C. A. Oliveira
Summary: The photocatalytic production of gamma-valerolactone from levulinic acid was achieved using UV-assisted accumulated electron transfer technique. A commercial niobic acid was used as the photocatalyst, showing higher efficiency in ethanol as a hole scavenger and additional contact time with the substrate. By optimizing the reaction conditions, longer illumination time resulted in higher selectivity towards the desired product.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Article
Chemistry, Multidisciplinary
Nikolaos Kaplaneris, Alejandro Puet, Felix Kallert, Julia Poehlmann, Lutz Ackermann
Summary: We achieved the late-stage diversification of structurally complex peptides through palladium-catalyzed C-H arylation. The tunability and ease of preparation of arylthianthrenium salts allowed us to forge sterically congested biaryl linkages between tryptophan-containing peptides and drug, natural product, and peptidic scaffolds. The robustness of the palladium catalysis regime was demonstrated by the full tolerance of sensitive and coordinating functional groups. As a result, we efficiently accessed highly decorated, labelled, conjugated, and ligated linear and cyclic peptides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jun Wu, Wen Wei, Julia Poehlmann, Rajeshwaran Purushothaman, Lutz Ackermann
Summary: In this study, a ruthenium(II)-catalyzed multicomponent Domino reaction was reported, which enables the efficient synthesis of structurally diversified C-alkyl glycosides in a single step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Dingyi Wang, Binbin Yuan, Jiawei Xu, Lutz Ackermann
Summary: In this study, an electrochemical strategy was used to achieve the dual functionalization of unactivated alkenes through an intramolecular migration process. This strategy eliminated the need for sacrificial chemical oxidants and noble-metal catalysts, and the reactions were carried out under mild conditions. The electrochemistry enabled the migration of (hetero)aryl groups, leading to the formation of alkenyl/alkynyl-migration products. The reaction mechanism was established through experiments and computations.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Editorial Material
Chemistry, Organic
Lutz Ackermann, Song Lin
Summary: The field of organic electrosynthesis and electrocatalysis has experienced a remarkable revival in recent years. Electrochemistry, as an unconventional reaction tool, has allowed synthetic chemists to innovate novel transformations, advance new synthetic strategies, and enhance the sustainability of organic synthesis.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Tristan von Muenchow, Suman Dana, Yang Xu, Binbin Yuan, Lutz Ackermann
Summary: Enantioselective oxidation reactions typically rely on costly transition metals and stoichiometric amounts of chemical oxidants. This study demonstrates a sustainable alternative by using electrocatalysis, specifically the hydrogen evolution reaction (HER), in place of a chemical oxidant. The use of cobalt catalyst for asymmetric oxidation enables highly enantioselective aryl carbon-hydrogen bond (C-H) activation reactions, leading to the synthesis of chiral compounds. Additionally, cobalt-mediated electrocatalysis allows for selective desymmetrization through dehydrogenative C-H activation reactions, facilitating the preparation of sterically complex phosphorus (P)-stereogenic compounds.
Review
Chemistry, Multidisciplinary
Dario Marchionni, Sumon Basak, Alireza Nazari Khodadadi, Assunta Marrocchi, Luigi Vaccaro
Summary: The past decade has witnessed a renewed interest in borazines and BN-doped polycyclic aromatic hydrocarbons due to their potential in various applications. This review critically examines the synthesis methods of (substituted) B3N3 motifs and focuses on the discussion of borazine-doped carbon structures developed for materials science applications.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Agnese Zangarelli, Binbin Yuan, Lutz Ackermann
Summary: The first electro-C7-alkenylation of indoles is reported in this study, providing highly selective access to the C7 position. This sustainable method avoids the use of toxic and expensive chemical oxidants and allows for versatile product diversification.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Editorial Material
Chemistry, Organic
Margaret A. Brimble, Lutz Ackermann, Yan-Mei Li, Monika Raj
Article
Chemistry, Physical
Julia Struwe, Lutz Ackermann
Summary: In recent years, photoelectrocatalysis has become more and more viable for molecular synthesis. However, there is still a lack of detailed comparison among different catalysts for the undirected C-H functionalization of arenes. To address this, more than a dozen different mediators were utilized to compare their efficacies in the trifluoromethylation of (hetero-)arenes.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Multidisciplinary
Giulia Brufani, Federica Valentini, Gabriele Rossini, Lucia Rosignoli, Yanlong Gu, Ping Liu, Luigi Vaccaro
Summary: Metal contamination is a significant problem in chemical synthesis, especially for products with biological activity. The use of appropriate operating conditions, such as a copper tube flow reactor (CTFR), can greatly reduce metal leaching and waste generation. A waste-minimized continuous flow process for synthesizing 1,4-disubstituted β-keto 1,2,3-triazoles was developed, which demonstrated low environmental impact through the measurement of various green metrics.
GREEN SYNTHESIS AND CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Isaac Maksso, Ramesh C. Samanta, Yifei Zhan, Kai Zhang, Svenja Warratz, Lutz Ackermann
Summary: The chemical up-cycling of polymers into value-added materials provides an opportunity for a circular economy. This study demonstrates the selective up-cycling of polystyrenes and polyolefins to C(sp(3))-H azidated materials through chemo-selective mangana-electrocatalysis. The functionalized polymers obtained showed high mass retention and functionalization. The electrocatalysis approach proved to be scalable and has implications for a green hydrogen economy.
Article
Chemistry, Multidisciplinary
Tsuyoshi Oyama, Lorena Mendive-Tapia, Verity Cowell, Adelina Kopp, Marc Vendrell, Lutz Ackermann
Summary: Fluorescent labeling of peptides catalyzed by non-toxic manganese(i) via C(sp(2))-H alkenylation enables the selective and site-specific labeling of peptides, providing access to novel near-infrared nitrobenzodiazole-based peptide fluorogenic probes.
Article
Chemistry, Multidisciplinary
Yan Zhang, Zhenzhi Cai, Chunhang Zhao, Hanliang Zheng, Lutz Ackermann
Summary: Electrooxidative radical cascade cyclization of 1,6-enynes enables the synthesis of sulfonamides with medium-sized rings. The activation barrier difference between alkynyl and alkenyl moieties allows for chemo-selective addition and regioselective ring formation. This metal-free and chemical oxidant-free reaction provides efficient access to sulfonamides with bridged or fused ring systems.
Article
Chemistry, Multidisciplinary
Jian-Biao Liu, Xiao-Jun Liu, Joao C. A. Oliveira, De-Zhan Chen, Lutz Ackermann
Summary: In this study, a radical-type migratory insertion involving synchronous but asynchronous metal-carbon (M-C) bond homolysis and radical attack was discovered through computations. Inspired by this radical migratory insertion, a distinct cobalt-catalyzed radical-mediated carbon-carbon (C-C) cleavage mechanism was proposed for alkylidenecyclopropanes (ACPs). This unique C-C activation mechanism plays a key role in explaining the experimentally observed selectivity for the coupling between benzamides and ACPs. Additionally, the C(sp(2))-H activation in the coupling reaction occurs via the proton-coupled electron transfer (PCET) mechanism instead of the originally proposed concerted metalation-deprotonation (CMD) pathway. The ring opening strategy may lead to further development and discovery of novel radical transformations.
Article
Chemistry, Multidisciplinary
Jose Luis Osorio-Tejada, Francesco Ferlin, Luigi Vaccaro, Volker Hessel
Summary: Carbon-to-carbon (C-C) cross-coupling reaction (CCR) protocols are a major breakthrough in synthetic chemistry, widely used in medicinal chemistry and other applied sciences. This study uses life cycle assessment (LCA) to evaluate the environmental impact of CCRs, separating intrinsic and extrinsic impacts. The findings suggest the need to recycle the catalyst, carefully choose the halobenzene, and recycle the ligand along with the catalyst.