The Groebke–Blackburn–Bienaymé reaction in its maturity: innovation and improvements since its 21st birthday (2019–2023)

• Cristina Martini,
• Muhammad Idham Darussalam Mardjan and
• Andrea Basso

Beilstein J. Org. Chem. 2024, 20, 1839–1879, doi:10.3762/bjoc.20.162

• compounds or molecules derived from biomass have been recently published. Due to the relatively drastic conditions of the GBB reaction and the inherent lability of these structurally complex building blocks, often specific reaction conditions have been developed to successfully obtain the multicomponent

• , the use of 5-HMF (23) [36], a renewable carbon source derived from biomass, responds to these requirements. This aldehyde displays additional functionalities useful for further modifications of the GBB adducts, but some optimization was necessary due to its intolerance to high temperatures and

Polymer degrading marine Microbulbifer bacteria: an un(der)utilized source of chemical and biocatalytic novelty

• Weimao Zhong and
• Vinayak Agarwal

Beilstein J. Org. Chem. 2024, 20, 1635–1651, doi:10.3762/bjoc.20.146

• structural similarity to two other β-agarases, ZgAgaA and ZgAgaB, from Zobellia galactanivorans, which is a model marine bacterium for the bioconversion of algal biomass [29][107][108][109]. The crystal structure suggested that the thermostability of rAgaA likely derives from the numerous surface salt

• -linked homopolymer of N-acetyl-β-ᴅ-glucosamine (GlcNAc), the second most abundant biomass on earth after cellulose (Figure 4). Approximately 1011 tons of chitin are produced annually in nature, about 70% of which originate from the ocean. Most of the chitin is recycled by bacteria and fungi as carbon and

Electrophotochemical metal-catalyzed synthesis of alkylnitriles from simple aliphatic carboxylic acids

• Yukang Wang,
• Yan Yao and
• Niankai Fu

Beilstein J. Org. Chem. 2024, 20, 1497–1503, doi:10.3762/bjoc.20.133

• ][18]. Owing to the prevalence of aliphatic carboxylic acids in biomass and natural products, decarboxylative cyanation represents one of the most straightforward and attractive approaches to accessing alkylnitriles [19][20]. As an elegant example, Barton demonstrated the application of redox-active

Sustainable tandem acylation/Diels–Alder reaction toward versatile tricyclic epoxyisoindole-7-carboxylic acids in renewable green solvents

• Ayhan Yıldırım

Beilstein J. Org. Chem. 2024, 20, 1308–1319, doi:10.3762/bjoc.20.114

• among the main sources of serious environmental problems [2]. However, the risk of depletion of these resources in the near future has led researchers to research and develop safer, environmentally friendly and renewable resources [3][4][5]. Biomass is an important and more economical renewable source

Manganese-catalyzed C–C and C–N bond formation with alcohols via borrowing hydrogen or hydrogen auto-transfer

• Mohd Farhan Ansari,
• Atul Kumar Maurya,
• Abhishek Kumar and
• Saravanakumar Elangovan

Beilstein J. Org. Chem. 2024, 20, 1111–1166, doi:10.3762/bjoc.20.98

• friendly and atom-economical process for C–C and C–N bond formations utilizing alcohol as an alkylating agent and hydrogen donor, producing water as the only side-product [6][7][8][9]. Notably, alcohols are inexpensive, abundant and can be obtained from biomass, which makes this method even more attractive

Skeletal rearrangement of 6,8-dioxabicyclo[3.2.1]octan-4-ols promoted by thionyl chloride or Appel conditions

• Martyn Jevric,
• Julian Klepp,
• Johannes Puschnig,
• Oscar Lamb,
• Christopher J. Sumby and
• Ben W. Greatrex

Beilstein J. Org. Chem. 2024, 20, 823–829, doi:10.3762/bjoc.20.74

• ) is produced selectively when cellulose-containing materials, including lignocellulosic biomass, are acidified and pyrolysed [1][2]. Lab scale synthesis of this chiral material can be accomplished in a single step without special glassware [3], while large scale production of the reduction product

Synthesis of 5-arylidenerhodanines in L-proline-based deep eutectic solvent

• Stéphanie Hesse

Beilstein J. Org. Chem. 2023, 19, 1537–1544, doi:10.3762/bjoc.19.110

• potential of those solvents in many applications (electrodeposition, organic syntheses, biomass extraction, etc.) [11][12]. The more recent ones also deal with the importance of a better characterization of DES [13] and a clear evaluation of their sustainability via life-cycle assessment to evaluate the

• formation of the expected 5-benzylidenerhodanine 3i under the optimized conditions with a slightly lower yield (3i versus 3a). Finally, we also decided to investigate the reactivity of 5-hydroxymethylfurfural (HMF). Indeed, HMF is considered as one of the most promising biomass-derived platform chemicals

Non-noble metal-catalyzed cross-dehydrogenation coupling (CDC) involving ether α-C(sp³)–H to construct C–C bonds

• Hui Yu and
• Feng Xu

Beilstein J. Org. Chem. 2023, 19, 1259–1288, doi:10.3762/bjoc.19.94

• CDC reaction to be a new generation method for the construction of C–C bonds and it has received extensive attention and in-depth research [16][17][18][19][20][21][22][23][24]. The building blocks of ethers are widely found in biomass, chemical feedstocks, biologically active drugs, and natural

Photoredox catalysis harvesting multiple photon or electrochemical energies

• Mattia Lepori,
• Simon Schmid and
• Joshua P. Barham

Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81

Photoredox catalysis enabling decarboxylative radical cyclization of γ,γ-dimethylallyltryptophan (DMAT) derivatives: formal synthesis of 6,7-secoagroclavine

• Alessio Regni,
• Francesca Bartoccini and
• Giovanni Piersanti

Beilstein J. Org. Chem. 2023, 19, 918–927, doi:10.3762/bjoc.19.70

• ][32][33], modification of biomacromolecules [34], and relatively complex pharmaceutical agents [35][36][37][38]. Photocatalysis tremendously enriches the synthetic compound library, providing a precious alternative to directly modify abundant natural substrates, including biomass, which usually

C3-Alkylation of furfural derivatives by continuous flow homogeneous catalysis

• Grédy Kiala Kinkutu,
• Catherine Louis,
• Myriam Roy,
• Juliette Blanchard and
• Julie Oble

Beilstein J. Org. Chem. 2023, 19, 582–592, doi:10.3762/bjoc.19.43

• formation of the imine directing group and the C3-functionalization with some vinylsilanes and norbonene. Keywords: biomass; C–H activation; flow; furfural; homogeneous catalysis; Introduction The conversion of biomass derivatives into value-added products is one of the key branches of green chemistry and

Oxa-Michael-initiated cascade reactions of levoglucosenone

• Julian Klepp,
• Thomas Bousfield,
• Hugh Cummins,
• Sarah V. A.-M. Legendre,
• Jason E. Camp and
• Ben W. Greatrex

Beilstein J. Org. Chem. 2022, 18, 1457–1462, doi:10.3762/bjoc.18.151

• derived from biomass pyrolysis, due to its reactive functionality, and the chirality which derives from glucose [4][5][6][7]. Reactions of 1 where the α,β-unsaturated ketone participates as an electrophile are usually completely diastereoselective, as the approach of the nucleophile is controlled by the

• ]. The reaction is interesting as both furfural and 1 are present along with water in crude biomass pyrolysates, and so the reaction could affect yields of 1 [3][17][18]. Samet and co-workers have reported a similar condensation of 1 with salicylaldehyde resulting in chiral chromene derivative 4 [19][20

• approximate 90° dihedral angle. Conclusion This work has described a novel reaction of a cyclic biomass-derived α,β-unsaturated ketone with aromatic aldehydes. The ready availability of levoglucosenone in large quantities from biomass could make compounds such as 5 of interest for green chiral materials

Modular synthesis of 2-furyl carbinols from 3-benzyldimethylsilylfurfural platforms relying on oxygen-assisted C–Si bond functionalization

• Sebastien Curpanen,
• Per Reichert,
• Gabriele Lupidi,
• Giovanni Poli,
• Julie Oble and
• Alejandro Perez-Luna

Beilstein J. Org. Chem. 2022, 18, 1256–1263, doi:10.3762/bjoc.18.131

• biomass-derived furfural and 5-methylfurfural, are converted into 3-silylated 2-furyl carbinols upon condensation with organomagnesium or organolithium reagents. The hydroxy unit of the carbinol adducts can be exploited to promote C3(sp2)–Si bond functionalization through intramolecular activation. Two

• carbinols from renewable feedstock. Keywords: biomass; copper; cyclic siloxanes; 2-furyl carbinols; silicon; Introduction Progress towards the use of nonedible renewable feedstock to replace fossil resources as starting material for high-value chemicals is an important endeavor of modern synthesis [1][2

• , we have demonstrated that C3-benzyldimethylsilyl-appended furfurals are useful platforms that offer modular access to 3-substituted 2-furyl carbinols. This strategy represents a new, simple, and selective way to decorate the biomass-derived furan nucleus, allowing to reach synthetically relevant

Polymer and small molecule mechanochemistry: closer than ever

• José G. Hernández

Beilstein J. Org. Chem. 2022, 18, 1225–1235, doi:10.3762/bjoc.18.128

• -free ball milling has enabled to surpass the insolubility and recalcitrant reactivity of cellulose [36][37], chitin [38][39], and lignin (Figure 2) [40][41]. In addition to allowing solvent-free reactions, mechanical forces generated inside ball mills can depolymerize biomass through cleavage pathways

Synthesis of tryptophan-dehydrobutyrine diketopiperazine and biological activity of hangtaimycin and its co-metabolites

• Houchao Xu,
• Anne Wochele,
• Minghe Luo,
• Gregor Schnakenburg,
• Yuhui Sun,
• Heike Brötz-Oesterhelt and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2022, 18, 1159–1165, doi:10.3762/bjoc.18.120

• species B. subtilis 168 and of B) nosocomial pathogen A. baumannii 09987 monitored by recording the turbidity increase of growing culture aliquots exposed to a concentration series of 1 every 10 min over 24 h. An increase in the optical density at 600 nm (OD600) reflects biomass production. At

Identification of the new prenyltransferase Ubi-297 from marine bacteria and elucidation of its substrate specificity

• Jamshid Amiri Moghaddam,
• Huijuan Guo,
• Karsten Willing,
• Thomas Wichard and
• Christine Beemelmanns

Beilstein J. Org. Chem. 2022, 18, 722–731, doi:10.3762/bjoc.18.72

• (final concentration of 0.1 mM). After 12 h, 8-HQA, farnesol, and MgCl2 were added to the fermentation with a final concentration of 1 mM. Fermentation was continued for 3 d at 30 °C, after which the culture was centrifuged and the cell biomass was lyophilized. Dry cell mass (103.6 g) was extracted with

Inductive heating and flow chemistry – a perfect synergy of emerging enabling technologies

• Conrad Kuhwald,
• Sibel Türkhan and
• Andreas Kirschning

Beilstein J. Org. Chem. 2022, 18, 688–706, doi:10.3762/bjoc.18.70

• process because a rapid and uniform heating of the biomass and catalyst is important for product quality. Compared to a conventional heating process, the authors found that a higher quality of bio-oil with a higher yield of aromatic hydrocarbons and a lower oxygen content is obtained in a process with RF

• (reaction 1) and steam (reaction 2) methane reforming. Calcination and RF heating. The continuously operated “Sabatier” process. Biofuel production from biomass using inductive heating for pyrolysis. Water electrolysis using an inductively heated electrolysis cell. Dimroth rearrangement (reaction 1) and

Antiviral therapy in shrimp through plant virus VLP containing VP28 dsRNA against WSSV

• Santiago Ramos-Carreño,
• Ivone Giffard-Mena,
• Jose N. Zamudio-Ocadiz,
• Alfredo Nuñez-Rivera,
• Ricardo Valencia-Yañez,
• Jaime Ruiz-Garcia,
• Maria Teresa Viana and
• Ruben D. Cadena-Nava

Beilstein J. Org. Chem. 2021, 17, 1360–1373, doi:10.3762/bjoc.17.95

• salinity) at 28 ± 1 °C, oxygen > 5.0 mg/L, pH 7.6 ± 0.16 and ammonium < 0.5 mg/L. The postlarvae were fed a commercial diet (Natural Force 35® VIMIFOS, Mexico) at 5% of the total biomass thrice a day. The seawater was filtered (10.5 and 5 µm sediment water filters, respectively), exposed to UV and aerated

• 12 h light and 12 h dark was used. The shrimp were fed with a commercial diet twice a day at 3% of their biomass. Shrimp were gradually acclimatized to 16 ppt and kept 15 days in observation before starting the experiment. Filters containing activated carbon were used to maintain an optimum seawater

• . Before the infection per os, fasted shrimp for 24 hours were fed twice a day with infected ground tissue (≈10 biomass) [46]. Six hours after the last dose, the unconsumed infected tissue was removed, and aquarium water was replaced, per Thomas et al. [49]. Mortality was recorded to register the dose

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

• Guido Gambacorta,
• James S. Sharley and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90

Valorisation of plastic waste via metal-catalysed depolymerisation

• Francesca Liguori,
• Carmen Moreno-Marrodán and
• Pierluigi Barbaro

Beilstein J. Org. Chem. 2021, 17, 589–621, doi:10.3762/bjoc.17.53

• turn a challenge into an opportunity [24][25]. The waste-to-products strategy is already in place for both animal [26][27] and plant biomass polymeric waste [28][29], for which mature technologies are operative [30]. When referring to polymers in general, there is often a lack of univocal definitions

• , we will use the term “depolymerisation” to identify the “process of converting a macromolecule into (recoverable) monomers or a mixture of monomers". Another relevant definition is that of “bioplastic”, meaning “biobased polymer derived from the biomass or issued from monomers derived from the

• biomass”, wherein “biobased” indicates “composed or derived in whole or in part of biological products issued from the biomass”. Also, there is no universally accepted definition for “compostable”, as it differs between diverse issuers [34]. The criteria indicated by the European Commission through the

¹⁹F NMR as a tool in chemical biology

• Diana Gimenez,
• Aoife Phelan,
• Cormac D. Murphy and
• Steven L. Cobb

Beilstein J. Org. Chem. 2021, 17, 293–318, doi:10.3762/bjoc.17.28

• pesticide cyhalothrin [106] by the fungus Cunninghamella elegans. In the former, 19F NMR demonstrated the appearance of phase 1 (oxidative) and phase 2 (conjugative) metabolites, and in the latter, it was possible to monitor the migration of the pesticide into the biomass in the first 24 h after its

A novel and robust heterogeneous Cu catalyst using modified lignosulfonate as support for the synthesis of nitrogen-containing heterocycles

• Bingbing Lai,
• Meng Ye,
• Ping Liu,
• Minghao Li,
• Rongxian Bai and
• Yanlong Gu

Beilstein J. Org. Chem. 2020, 16, 2888–2902, doi:10.3762/bjoc.16.238

• and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. China 10.3762/bjoc.16.238 Abstract A waste biomass, sodium lignosulfonate, was treated with sodium 2-formylbenzenesulfonate, and the phenylaldehyde condensation product was then used as

• tricyclic indoles bearing 3,4-fused seven-membered rings, 2‑arylpyridines, aminonaphthalenes and 3-phenylisoquinolines. In addition, this catalyst showed to be recyclable and could be reused several times without significant loss in activity during the course of the reaction process. Keywords: biomass

Palladium nanoparticles supported on chitin-based nanomaterials as heterogeneous catalysts for the Heck coupling reaction

• Tony Jin,
• Malickah Hicks,
• Davis Kurdyla,
• Sabahudin Hrapovic,
• Edmond Lam and
• Audrey Moores

Beilstein J. Org. Chem. 2020, 16, 2477–2483, doi:10.3762/bjoc.16.201

• Mining and Materials Engineering, McGill University, Montreal, Quebec H3A 0E9, Canada 10.3762/bjoc.16.201 Abstract In this report, chitin and chitosan nanocrystals were used as biomass-based supports for Pd nanoparticles (NPs) used as a heterogeneous catalyst for the Heck coupling reaction. By using a

• benign conditions, outcompeting the use of other catalysts supported on biomass-based nanomaterials, including cellulose nanocrystals. These initial results show the potential for using chitinous nanomaterials as effective catalyst supports in cross-coupling reactions. Keywords: chitin; chitosan; Heck

• coupling; heterogeneous catalysis; nanomaterial; Introduction Over the past decades, biomass-based nanomaterials have become a highly prevalent topic of research owing to their sustainability, bioavailability, unique structural and morphological characteristics [1]. Particularly dominant in this field are

A proposed sustainability index for synthesis plans based on input provenance and output fate: application to academic and industrial synthesis plans for vanillin as a case study

• John Andraos

Beilstein J. Org. Chem. 2020, 16, 2346–2362, doi:10.3762/bjoc.16.196

• of the target product that is actually used for its intended purpose. Renewable energy sources are defined as originating from hydroelectric, wind, solar, geothermal, and biomass sources. The computation of SI is illustrated for 22 synthesis plans of the high commodity flavour ingredient vanillin

• metrics defined for biomass-based carbon chemicals using ethanol equivalent as a common basis: sustainability value of resource replacement, sustainability value of the fate of waste, and sustainability indicator [5][6][7]. Sikdar defined sustainability as the interplay of three domains: economic aspects

• , environmental aspects, and social aspects [8]. Sheldon and Sanders defined sustainability metrics for the production of chemicals from renewable biomass in terms of four criteria: material and energy efficiency, land use, and process economics [9]. Very recently, Egyptian and Lebanese scientists put forward an

One-pot synthesis of isosorbide from cellulose or lignocellulosic biomass: a challenge?

• Isaline Bonnin,
• Raphaël Mereau,
• Thierry Tassaing and
• Karine De Oliveira Vigier

Beilstein J. Org. Chem. 2020, 16, 1713–1721, doi:10.3762/bjoc.16.143

• ; isosorbide; lignocellulosic biomass; Introduction Cellulose, a homopolymer of ᴅ-glucose, is the most abundant component of lignocellulosic biomass. Cellulose is a crystalline polymer due to its intra- and intermolecular hydrogen bond network. The conversion of cellulose to added value chemicals has received

• to sorbitol and 3) dehydration of sorbitol to isosorbide (Scheme 1). Isosorbide, a molecule obtained from biomass can find many applications such as additives, pharmaceuticals [2][3] and monomers for polymer industries [4][5][6]. For instance, one polymer obtained from isosorbide, poly(ethylene-co

• step reported in the literature, several researchers investigated the direct conversion of cellulose or lignocellulosic biomass to isosorbide. Several strategies were employed such as a combination of homogeneous acid and supported metal catalyst, or a combination of supported metal catalyst and solid