Palladium-catalyzed three-component radical-polar crossover carboamination of 1,3-dienes or allenes with diazo esters and amines

• Geng-Xin Liu,
• Xiao-Ting Jie,
• Ge-Jun Niu,
• Li-Sheng Yang,
• Xing-Lin Li,
• Jian Luo and
• Wen-Hao Hu

Beilstein J. Org. Chem. 2024, 20, 661–671, doi:10.3762/bjoc.20.59

• . Multicomponent reactions (MCRs) by virtue of high efficiency for the construction of complex chemicals, have shown the superiority in high step and atom economy in organic synthesis [25][26][27]. Over the past two decades, our group and others have developed a transition-metal-catalyzed MCR strategy involving

HPW-Catalyzed environmentally benign approach to imidazo[1,2-a]pyridines

• Luan A. Martinho and
• Carlos Kleber Z. Andrade

Beilstein J. Org. Chem. 2024, 20, 628–637, doi:10.3762/bjoc.20.55

• ][21][22]. Multicomponent reactions (MCRs) provide one-pot reactions, simple synthetic procedures, less waste being produced, fewer purification steps, and a high atom economy [23]. The GBB three-component reaction is carried out in the presence of Lewis or Brønsted acid catalysis to increase the

Recent advancements in iodide/phosphine-mediated photoredox radical reactions

• Tinglan Liu,
• Yu Zhou,
• Junhong Tang and
• Chengming Wang

Beilstein J. Org. Chem. 2023, 19, 1785–1803, doi:10.3762/bjoc.19.131

• notable advantages in terms of both step- and atom-economy. Taking inspiration from the groundbreaking work of Shang and Fu [6], Li and colleagues demonstrated an innovative approach for the photocatalytic [3 + 2] and [4 + 2] annulation of enynals 32 and γ,σ-unsaturated N-(acyloxy)phthalimides 33 (Scheme

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

• synthetic strategy for the construction of C–C bonds in organic synthesis (Scheme 1b). Compared with traditional coupling reactions, the CDC strategy has the following advantages: 1) atom economy, 2) green and efficient reaction, 3) a wide range of substrate sources. Therefore, organic chemists consider the

• operation, wide substrate range, and atom economy. It provides a new strategy for constructing functionalized pyridines. The reaction undergoes the following four processes: initially, DTBP is decomposed into two tert-butylperoxyl radicals A under heat. Then, the tert-butylperoxyl radical converts the ether

Acetaldehyde in the Enders triple cascade reaction via acetaldehyde dimethyl acetal

• Alessandro Brusa,
• Debora Iapadre,
• Maria Edith Casacchia,
• Alessio Carioscia,
• Giuliana Giorgianni,
• Giandomenico Magagnano,
• Fabio Pesciaioli and
• Armando Carlone

Beilstein J. Org. Chem. 2023, 19, 1243–1250, doi:10.3762/bjoc.19.92

• reason, the use of MCRs is appealing in the construction of natural or synthetic products [2][3][4][5] or libraries of compounds [2], and is generally considered an advantage in organic synthesis for atom economy, waste reduction and time saving. Cascade reactions are defined as chemical processes in

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

Honeycomb reactor: a promising device for streamlining aerobic oxidation under continuous-flow conditions

• Masahiro Hosoya,
• Yusuke Saito and
• Yousuke Horiuchi

Beilstein J. Org. Chem. 2023, 19, 752–763, doi:10.3762/bjoc.19.55

• , which diminishes the atom economy [2]. To overcome this limitation, the use of molecular oxygen (O2) present in air as an oxidant is one of the ideal solutions [10][11]. The reduction of O2 generates only water as a byproduct, leading to high atom-economy processes. However, the use of O2 as an oxidant

A new oxidatively stable ligand for the chiral functionalization of amino acids in Ni(II)–Schiff base complexes

• Alena V. Dmitrieva,
• Oleg A. Levitskiy,
• Yuri K. Grishin and
• Tatiana V. Magdesieva

Beilstein J. Org. Chem. 2023, 19, 566–574, doi:10.3762/bjoc.19.41

• , see Table 2); consequently, a stereoinduction efficiency expected for ligand L7 may be lower than that of L4. However, taking into account the simplicity of our procedure and the atom-economy principle, the ligand L7 can be considered as a cheaper alternative to L4, still providing a significant

Total synthesis of insect sex pheromones: recent improvements based on iron-mediated cross-coupling chemistry

• Eric Gayon,
• Guillaume Lefèvre,
• Olivier Guerret,
• Adrien Tintar and
• Pablo Chourreu

Beilstein J. Org. Chem. 2023, 19, 158–166, doi:10.3762/bjoc.19.15

• to overall processes with a low atom economy, generating a significant amount of chemical waste, and which can be expensive when noble metals such as palladium salts are required (Scheme 1). The high efficiency of transition-metal-catalyzed cross-coupling methods in C–C bond formation processes

• , dialkyl phosphates used as leaving groups lead to overall transformations which display a poor atom economy. Moreover, diethyl chlorophosphate (DCP), used as a classic starting material in the dienol phosphates synthesis, is also registered under REACH regulation, and its use brings several toxicity

• aimed at combining the advantages brought by those additives with the atom-economy offered by the use of organic electrophiles bearing halide leaving groups (better than that obtained with phosphates leaving groups, Scheme 4). We thus investigated the development of pheromone synthesis involving cross

Two-step continuous-flow synthesis of 6-membered cyclic iodonium salts via anodic oxidation

• Julian Spils,
• Thomas Wirth and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2023, 19, 27–32, doi:10.3762/bjoc.19.2

• continuous-flow procedure for the generation of six-membered diaryliodonium salts. The accompanying scalability and atom economy are significant improvements to existing batch methods. Benzyl acetates are submitted to this two-step procedure as highly available and cheap starting materials. An acid-catalyzed

• otherwise tedious to synthesize CDIS robustly in short reaction times. A significant drawback still is the use of stoichiometric amounts of chemical oxidants, which decreases the atom economy and necessitates additional workup procedures. A possible solution is the anodic oxidation of iodoarenes as

• alcohols as a solvent [37][38]. Therefore, we attempt to transfer our already established one-pot procedure towards CDIS 1 into a multi-step electrochemical flow process, improving reaction times, atom economy, and scalability (Scheme 1C). Results and Discussion We initially investigated the second step of

Combining the best of both worlds: radical-based divergent total synthesis

• Kyriaki Gennaiou,
• Antonios Kelesidis,
• Maria Kourgiantaki and
• Alexandros L. Zografos

Beilstein J. Org. Chem. 2023, 19, 1–26, doi:10.3762/bjoc.19.1

• of atom economy and protecting-group-free synthesis dominating the field of total synthesis. In this new era, total synthesis is moving towards natural efficacy by utilizing both the biosynthetic knowledge of divergent synthesis and the latest developments in radical chemistry. This contemporary

• of divergent synthesis, common synthetic scaffolds, which are regarded as the points of diversity of the synthetic plan, lie at the heart of retrosynthetic design. Radical disconnections on common scaffolds, in accordance to the trends of green chemistry [11] and the concepts of atom economy [12] and

One-pot double annulations to confer diastereoselective spirooxindolepyrrolothiazoles

• Juan Lu,
• Bin Yao,
• Desheng Zhan,
• Zhuo Sun,
• Yun Ji and
• Xiaofeng Zhang

Beilstein J. Org. Chem. 2022, 18, 1607–1616, doi:10.3762/bjoc.18.171

• separation (process A) and the single-step method (process B) for the synthesis of spirooxindolepyrrolothiazoles 5a according to the reaction conditions shown in Scheme 6. Green chemistry metrics data including atom economy (AE), atom efficiency (AEf), carbon efficiency (CE), reaction mass efficiency (RME

Cyclometalated iridium complexes-catalyzed acceptorless dehydrogenative coupling reaction: construction of quinoline derivatives and evaluation of their antimicrobial activities

• Hongling Shui,
• Yuhong Zhong,
• Renshi Luo,
• Zhanyi Zhang,
• Jiuzhong Huang,
• Ping Yang and
• Nianhua Luo

Beilstein J. Org. Chem. 2022, 18, 1507–1517, doi:10.3762/bjoc.18.159

• reactions have the advantages of high atom economy, simple operation, clean and green, and have become a research hotspot [31][32][33][34][35]. Cyclometalated iridium complexes with good catalytic efficiency and selectivity are very effective catalysts in ADC reactions. Moreover, these catalysts are easy to

Make or break: the thermodynamic equilibrium of polyphosphate kinase-catalysed reactions

• Michael Keppler,
• Sandra Moser,
• Henning J. Jessen,
• Christoph Held and
• Jennifer N. Andexer

Beilstein J. Org. Chem. 2022, 18, 1278–1288, doi:10.3762/bjoc.18.134

• the synthesis of ATP from adenosine uses an acetate kinase for the final conversion of ADP to ATP (Table 1) [45]. Acetylphosphate has long been preferred as phosphate donor over phosphoenolpyruvate in large-scale reactions, due to economic factors such as ease of production and atom economy [57]. On

Automated grindstone chemistry: a simple and facile way for PEG-assisted stoichiometry-controlled halogenation of phenols and anilines using N-halosuccinimides

• Dharmendra Das,
• Akhil A. Bhosle,
• Amrita Chatterjee and
• Mainak Banerjee

Beilstein J. Org. Chem. 2022, 18, 999–1008, doi:10.3762/bjoc.18.100

• dihalogenations. As known, the decarboxylation (or desulfonation) was observed in the case of salicylic acids and anthranilic acids (or sulfanilic acids) leading to 2,4,6-trihalogenated products when 3 equiv of NXS was used. Simple instrumentation, metal-free approach, cost-effectiveness, atom economy, short

• (X = Br, Cl) suffers from low atom economy (<50%), formation of corrosive byproducts (e.g., HBr) [15][16], which cause serious environmental issues. To mitigate the problem, several mild and operationally safe halogenating agents have been successfully introduced to replace X2 [17][18][19][20][21][22

Morita–Baylis–Hillman reaction of 3-formyl-9H-pyrido[3,4-b]indoles and fluorescence studies of the products

• Nisha Devi and
• Virender Singh

Beilstein J. Org. Chem. 2022, 18, 926–934, doi:10.3762/bjoc.18.92

• leading to the formation of allylic alcohol; a highly functionalized product [41][42][43][44]. The chemistry of the MBH reaction is decorated with several unique features viz. atom economy, complexity generation and generation of a chiral center from a pro-chiral electrophile. The chemistry of the MBH

Menadione: a platform and a target to valuable compounds synthesis

• Acácio S. de Souza,
• Ruan Carlos B. Ribeiro,
• Dora C. S. Costa,
• Fernanda P. Pauli,
• David R. Pinho,
• Matheus G. de Moraes,
• Fernando de C. da Silva,
• Luana da S. M. Forezi and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 381–419, doi:10.3762/bjoc.18.43

• Ti-based [65][67], Nb-based [68][69], and Au-based [70] heterogeneous systems. In addition to being more efficient, given the obtained atom economy, the reactions that use these catalytic heterogeneous systems are also presented as environmentally friendly. They are cleaner, either because of the low

Regioselectivity of the S_EAr-based cyclizations and S_EAr-terminated annulations of 3,5-unsubstituted, 4-substituted indoles

• Jonali Das and
• Sajal Kumar Das

Beilstein J. Org. Chem. 2022, 18, 293–302, doi:10.3762/bjoc.18.33

• generated via 1,6-hydride shift in both I and II. Finally, an intramolecular Mannich-type cyclization then furnishes products 27. The cascade protocol enjoys several advantageous synthetic features, including high step- and atom-economy, transition-metal-free and room temperature conditions. In all cases

Iron-catalyzed domino coupling reactions of π-systems

• Austin Pounder and
• William Tam

Beilstein J. Org. Chem. 2021, 17, 2848–2893, doi:10.3762/bjoc.17.196

• products and processes that reduce or eliminate the use and generation of hazardous substances, as well as increase the atom economy of the reaction [9]. Among the transition-metal (TM) catalysts often used, the late transition metals like rhodium [10][11][12][13][14], palladium [15][16][17][18][19

Synthetic strategies toward 1,3-oxathiolane nucleoside analogues

• Umesh P. Aher,
• Dhananjai Srivastava,
• Girij P. Singh and
• Jayashree B. S

Beilstein J. Org. Chem. 2021, 17, 2680–2715, doi:10.3762/bjoc.17.182

Photoredox catalysis in nickel-catalyzed C–H functionalization

• Lusina Mantry,
• Rajaram Maayuri,
• Vikash Kumar and
• Parthasarathy Gandeepan

Beilstein J. Org. Chem. 2021, 17, 2209–2259, doi:10.3762/bjoc.17.143

• powerful tool in organic synthesis, they generally require prefunctionalized starting materials, which significantly affect the reaction's atom economy and produce inorganic, organometallic salt wastes [23][24][25]. During the last decade, the oxidative functionalization of inert C‒H into carbon–carbon (C

Development of N-F fluorinating agents and their fluorinations: Historical perspective

• Teruo Umemoto,
• Yuhao Yang and
• Gerald B. Hammond

Beilstein J. Org. Chem. 2021, 17, 1752–1813, doi:10.3762/bjoc.17.123

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

• the compatibility of the flow approach with a green chemical manufacturing future. It is also not difficult to see how continuous manufacturing has implications for important green chemistry metrics such as atom economy, reaction mass efficiency, effective mass yield, carbon efficiency and

Nitroalkene reduction in deep eutectic solvents promoted by BH₃NH₃

• Chiara Faverio,
• Monica Fiorenza Boselli,
• Patricia Camarero Gonzalez,
• Alessandra Puglisi and
• Maurizio Benaglia

Beilstein J. Org. Chem. 2021, 17, 1041–1047, doi:10.3762/bjoc.17.83

• nitroalkanes, valuable precursors of amines. A variety of nitrostyrenes and alkyl-substituted nitroalkenes, including α- and β-substituted nitroolefins, were chemoselectively reduced to the nitroalkanes, with an atom economy-oriented, simple and convenient experimental procedure. A reliable and easily

• reproducible protocol to isolate the product without the use of any organic solvent was established, and the recyclability of the DES mixture was successfully investigated. Keywords: alternative solvents; atom economy; DES; nitro derivatives; reduction; Introduction The search for alternative solvents, not

• materials that can be used to form eutectic mixtures offers an incredibly high variety of combinations to generate new, safe and biodegradable DESs [5]. Another fundamental principle of green chemistry is the atom economy concept. In this context, ammonia borane (AB) is receiving increasing attention as

Synthetic accesses to biguanide compounds

• Oleksandr Grytsai,
• Cyril Ronco and
• Rachid Benhida

Beilstein J. Org. Chem. 2021, 17, 1001–1040, doi:10.3762/bjoc.17.82

• biguanides. This pathway is particularly convenient as cyanoguanidines are readily available, inexpensive, and safe [32]. Moreover, this reaction occurs with full atom economy and provides the desired biguanides with fairly high yields. A prior step of substituted cyanoguanidine preparation gives access to