Metal-free glycosylation with glycosyl fluorides in liquid SO₂

• Krista Gulbe,
• Jevgeņija Lugiņina,
• Edijs Jansons,
• Artis Kinens and
• Māris Turks

Beilstein J. Org. Chem. 2021, 17, 964–976, doi:10.3762/bjoc.17.78

• , often heavy metals; (2) multiple additives (co-promoter, molecular sieves, acid scavenger) to facilitate the reaction and/or suppress formation of side-products; (3) low temperatures; (4) complex experimental procedures. Additionally, the majority of the methods reported to date have been applied only

Manganese/bipyridine-catalyzed non-directed C(sp³)–H bromination using NBS and TMSN₃

• Kumar Sneh,
• Takeru Torigoe and
• Yoichiro Kuninobu

Beilstein J. Org. Chem. 2021, 17, 885–890, doi:10.3762/bjoc.17.74

• -position of an oxazoline or amide is selectively activated using a copper or palladium catalyst. Manganese is one of the most abundant and nontoxic transition metals found in the earth’s crust and its corresponding complexes and salts are useful in synthetic organic reactions [29][30][31][32][33][34][35

Highly regio- and stereoselective phosphinylphosphination of terminal alkynes with tetraphenyldiphosphine monoxide under radical conditions

• Dat Phuc Tran,
• Yuki Sato,
• Yuki Yamamoto,
• Shin-ichi Kawaguchi,
• Shintaro Kodama,
• Akihiro Nomoto and
• Akiya Ogawa

Beilstein J. Org. Chem. 2021, 17, 866–872, doi:10.3762/bjoc.17.72

• compounds in catalytic technologies, biochemistry, and materials [1][2][3][4][5][6]. In particular, in coordination chemistry and catalyst chemistry, organophosphorus compounds such as triorganylphosphines are widely used as typical monodentate ligands for many metals [7][8]. In addition, diphosphines such

• bidentate diphosphine ligands having a rigid structure and has increased attention as a useful and effective ligand in coordinating with various metals [19][20]. (Z)-Ph2PCH=CHPPh2 is very important as a bidentate ligand for many mononuclear complexes [21][22][23]. On the other hand, (E)-Ph2PCH=CHPPh2 acts

• as a monodentate ligand for mononuclear complexes, but it is highly attractive because a hierarchical structure can be constructed by cross-linking between two metals [24][25][26]. Considering the characteristics of the coordination form between the (E)- and (Z)-isomers, the development of a

Microwave-assisted multicomponent reactions in heterocyclic chemistry and mechanistic aspects

• Shivani Gulati,
• Stephy Elza John and
• Nagula Shankaraiah

Beilstein J. Org. Chem. 2021, 17, 819–865, doi:10.3762/bjoc.17.71

A chromatography-free and aqueous waste-free process for thioamide preparation with Lawesson’s reagent

• Ke Wu,
• Yichen Ling,
• An Ding,
• Liqun Jin,
• Nan Sun,
• Baoxiang Hu,
• Zhenlu Shen and
• Xinquan Hu

Beilstein J. Org. Chem. 2021, 17, 805–812, doi:10.3762/bjoc.17.69

• incomparable chelating ability towards selected transition metals, and the corresponding complexes were applied in various areas such as chemical-sensor materials, tunable redox-potential complexes, polymer hybrid luminescence materials, building blocks for multinuclear complexes, and as catalysts for cross

[2 + 1] Cycloaddition reactions of fullerene C₆₀ based on diazo compounds

• Yuliya N. Biglova

Beilstein J. Org. Chem. 2021, 17, 630–670, doi:10.3762/bjoc.17.55

• . Catalysis is the next area that is gaining an ever-increasing practical focus in the studies on the use of C60 and fullerene-containing materials [51]. A comparative analysis of the activity of fullerene-containing compounds and noble metals as dehydrogenation catalysts allows to consider the former as

• alternatives that favorably differ in cost. However, the efficiency is similar to the functional analogs of catalytic additives based on noble metals [52]. The presence of metal–fullerene chemical bonding results in catalysts that reliably provide high process selectivity due to the simultaneous adsorption of

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

• standard EN 13432 “Packaging–Requirements for packaging recoverable through composting and biodegradation” include disintegration (i.e., breakdown of material to particles of a defined size), biodegradability, absence of negative effects on the composting process and amount of heavy metals below given

• , wherein acetates, phosphates and chlorides of heavy metals (Ti, Zn, Mg, Co, Fe) or lead oxide are commonly used in the alcoholysis and glycolysis of polyesters [127][128]. Despite that these systems ensure high conversions and selectivity, shortcomings relate to the harsh reaction conditions, slow

• kinetics, cost of metals, toxicity, difficulty in catalyst reusing and need of downstream processing. Significant efforts have thus been made to develop greener and sustainable catalytic systems featuring high efficiency under mild conditions. The use of sodium carbonate or bicarbonate as ecofriendly

A new and efficient methodology for olefin epoxidation catalyzed by supported cobalt nanoparticles

• Lucía Rossi-Fernández,
• Viviana Dorn and
• Gabriel Radivoy

Beilstein J. Org. Chem. 2021, 17, 519–526, doi:10.3762/bjoc.17.46

• have been developed, most of them using expensive or scarce metals (Au or Pd [18][19][20][21], groups IV and V metal oxides [22][23]) and mainly through homogeneous catalytic processes [24][25][26]. From a practical, economic and environmental point of view, reusable heterogeneous catalysts based on

• earth-abundant transition metals are much more attractive, especially for industrial applications [27][28]. In recent years, many efforts have been made in finding new catalytic systems based on the use of low cost and abundant non-noble metals, and much attention have been paid to the development of Fe

• , Mn and mainly Co-based catalysts for olefin epoxidation. Besides their low cost and low toxicity, the choice of these metals is related to their known ability to activate dioxygen in natural processes catalyzed by metal-containing enzymes [29][30]. Despite that various homogeneous [31][32] and

Annulation of a 1,3-dithiole ring to a sterically hindered o-quinone core. Novel ditopic redox-active ligands

• Sergey V. Norkov,
• Anton V. Cherkasov,
• Andrey S. Shavyrin,
• Maxim V. Arsenyev,
• Viacheslav A. Kuropatov and
• Vladimir K. Cherkasov

Beilstein J. Org. Chem. 2021, 17, 273–282, doi:10.3762/bjoc.17.26

• coordination ability. The redox state of o-quinone (semiquinone or catechol) could be changed both as free species or when it is coordinated to a metal ion as a ligand. Thus, the redox isomerism phenomenon was reported for o-quinone complexes with both transition and non-transition metals [1][2][3]. The

• ). The values of coupling constants with these protons vary in the range of 0.18–0.30 G, they are highly sensitive to the nature of the metallofragment at the chelating dioxolene site. With metals tending to high ionicity in the bonding with the ligand we observed smaller values of coupling constants. o

• and CF3 groups are omitted for clarity. Synthetic pathways for the preparation of o-quinone derivatives with annulated 1,3-dithiole ring. The tentative pathway for the formation of o-quinone 7 with annulated thiete ring. Reactions of o-quinone 6a. Stepwise reduction of o-quinones with metals to

The preparation and properties of 1,1-difluorocyclopropane derivatives

• Kymbat S. Adekenova,
• Peter B. Wyatt and
• Sergazy M. Adekenov

Beilstein J. Org. Chem. 2021, 17, 245–272, doi:10.3762/bjoc.17.25

• -valent transition metals such as Pd(0) also have a valuable catalytic role, particularly because of their ability to participate in oxidative addition reactions and to form π-allyl complexes. In the absence of nucleophiles, homolysis of the distal C–C bond takes place under the effect of high temperature

Selective synthesis of α-organylthio esters and α-organylthio ketones from β-keto esters and sodium S-organyl sulfurothioates under basic conditions

• Jean C. Kazmierczak,
• Roberta Cargnelutti,
• Thiago Barcellos,
• Claudio C. Silveira and
• Ricardo F. Schumacher

Beilstein J. Org. Chem. 2021, 17, 234–244, doi:10.3762/bjoc.17.24

• , and related compounds. Some of them are catalyzed by expensive transition metals, such as gold, iridium, palladium, and titanium. More recently, the selective formation of C–S bonds using 1,3-dicarbonyl compounds, followed by a C–C bond cleavage has emerged as a versatile and less expensive protocol

Au(III) complexes with tetradentate-cyclam-based ligands

• Ann Christin Reiersølmoen,
• Thomas N. Solvi and
• Anne Fiksdahl

Beilstein J. Org. Chem. 2021, 17, 186–192, doi:10.3762/bjoc.17.18

• range of other transition metals. The utilization of gold in synthetic organic chemistry has become a topic of interest during the last decades, as evidenced by the increasing number of review articles published in this period [1][2][3][4][5][6][7][8]. Whereas both gold(I) and gold(III) are proven to be

• binding properties [25] and reactions with bovine serum albumin [27]. Cyclam is known as a tetraamino-macrocyclic ligand, which binds strongly to give complexes with many transition metal cations. While catalytic applications of square planar cyclam complexes are reported for metals, such as Ni [30][31

Insight into functionalized-macrocycles-guided supramolecular photocatalysis

• Minzan Zuo,
• Krishnasamy Velmurugan,
• Kaiya Wang,
• Xueqi Tian and
• Xiao-Yu Hu

Beilstein J. Org. Chem. 2021, 17, 139–155, doi:10.3762/bjoc.17.15

• a stabilizer to control the size and distribution of the NPs and are able to intensely regulate the photocatalytic performance. 5) To improve the sustainability, noble metals need to be replaced by earth-abundant metals. However, in most cases, earth-abundant metals have a lower photocatalytic

• activity compared to noble metals in supramolecular materials. Therefore, there is an urgent demand to search for earth-abundant metals with a high activity. In conclusion, investigations on macrocycle-based catalysis are still needed to effectively extend their potential applications to solve chemical

An atom-economical addition of methyl azaarenes with aromatic aldehydes via benzylic C(sp³)–H bond functionalization under solvent- and catalyst-free conditions

• Divya Rohini Yennamaneni,
• Vasu Amrutham,
• Krishna Sai Gajula,
• Rammurthy Banothu,
• Murali Boosa and
• Narender Nama

Beilstein J. Org. Chem. 2020, 16, 3093–3103, doi:10.3762/bjoc.16.259

• years, C−H bond functionalization catalyzed by transition metals received a strong emphasis, and other different catalytic systems have also been encouraged [16][17][18][19][20]. Huang and co-workers first realized the addition of alkylazaarenes directly to unsaturated bonds via C(sp3)–H

• , Yaragorla et al. published a review on C(sp3)–H bond functionalization of 2-methylazaarenes [39]. These strategies are proficient, but due to the involvement of drastic reaction conditions, the use of expensive reagents, toxic metals, harmful solvents, and tedious workup procedures, they need to be

Controlled decomposition of SF₆ by electrochemical reduction

• Sébastien Bouvet,
• Bruce Pégot,
• Stéphane Sengmany,
• Erwan Le Gall,
• Eric Léonel,
• Anne-Marie Goncalves and
• Emmanuel Magnier

Beilstein J. Org. Chem. 2020, 16, 2948–2953, doi:10.3762/bjoc.16.244

• reactive, corrosive and toxic [12]. Recent and really impressive works were devoted to the decomposition of sulfur hexafluoride using stoichiometric or catalytic amounts of metals (Rh, Ni, Pt) [13][14][15][16]. Organic derivatives (phosphines or bipyridine) proved efficient tools for the selective

Regioselective synthesis of heterocyclic N-sulfonyl amidines from heteroaromatic thioamides and sulfonyl azides

• Vladimir Ilkin,
• Vera Berseneva,
• Tetyana Beryozkina,
• Tatiana Glukhareva,
• Lidia Dianova,
• Wim Dehaen,
• Eugenia Seliverstova and
• Vasiliy Bakulev

Beilstein J. Org. Chem. 2020, 16, 2937–2947, doi:10.3762/bjoc.16.243

• synthesis of complexes of bis(sulfonyl amidines) 3aj–an with metals is in progress. 1H and 13C NMR spectra including 2D HMBC and HSQC experiments of compounds 3a–an, as well as high-resolution mass spectra are consistent with the proposed structures. Carbon signals of the amidine groups of compounds 3

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

• the catalyst during the recovery process (mass recovery 97.5%). In stark contrast, the two referential catalysts showed inferior recyclability (Figure 6b and 6c) not only because the mass loss but also the low stability and capacity of the metals. Conclusion A robust heterogeneous Cu catalyst was

Dawn of a new era in industrial photochemistry: the scale-up of micro- and mesostructured photoreactors

• Emine Kayahan,
• Mathias Jacobs,
• Leen Braeken,
• Leen C.J. Thomassen,
• Simon Kuhn,
• Tom van Gerven and
• M. Enis Leblebici

Beilstein J. Org. Chem. 2020, 16, 2484–2504, doi:10.3762/bjoc.16.202

Recent developments in enantioselective photocatalysis

• Callum Prentice,
• James Morrisson,
• Andrew D. Smith and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2020, 16, 2363–2441, doi:10.3762/bjoc.16.197

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

• converse rate condition is true. Specifically, inputs derived from renewable or recycled sources such as biomass, scrap metals, or retrieved byproducts from other processes are considered valorized, and inputs derived from non-renewable sources such as fossil fuels and virgin mineral ores are considered

• control of prices of crude oil, natural gas, and metals; whereas, disclosing accurate and up-to-date information can expose vulnerabilities among governments and investors that can be taken advantage of. Furthermore, deciding where to terminate a chain of resources, i.e., which material to designate as

Synthetic approaches to bowl-shaped π-conjugated sumanene and its congeners

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186

• of the vital modes in metal binding and a range of π-conjugated planar systems having ηn-binding to metals have been reported. In contrast, buckybowls have multiple coordination sites for instance the positions available in the polycyclic architecture and also because of the presence of concave or

• convex faces. Therefore, in recent years, the coordination of bowl-shaped molecules with the transition metals is of fundamental interest in the area of π-bowls chemistry since the first details of the metal complex of C60. In this context, Hirao’s group has reported the first example of Fe(η6-sumanene

Regioselective cobalt(II)-catalyzed [2 + 3] cycloaddition reaction of fluoroalkylated alkynes with 2-formylphenylboronic acids: easy access to 2-fluoroalkylated indenols

• Tatsuya Kumon,
• Miroku Shimada,
• Jianyan Wu,
• Shigeyuki Yamada and
• Tsutomu Konno

Beilstein J. Org. Chem. 2020, 16, 2193–2200, doi:10.3762/bjoc.16.184

• the most efficient and convenient protocols for the construction of various 2,3-disubstituted indene derivatives, such as indenols and indenamines (Scheme 1b) [23][24][25]. There have been numerous studies on the reaction with nonfluorinated alkynes under the influence of various transition metals

Efficient [(NHC)Au(NTf₂)]-catalyzed hydrohydrazidation of terminal and internal alkynes

• Maximillian Heidrich and
• Herbert Plenio

Beilstein J. Org. Chem. 2020, 16, 2080–2086, doi:10.3762/bjoc.16.175

• oxygen and nitrogen-containing molecules, which tend to be more difficult for catalytic transformations utilizing other transition metals [32][33][34][35][36]. The [LAu(NTf2)]-catalyzed reaction can be described by a general mechanism (Scheme 1), in which the coordination of LAu+ by the alkyne [37][38

Syntheses of spliceostatins and thailanstatins: a review

• William A. Donaldson

Beilstein J. Org. Chem. 2020, 16, 1991–2006, doi:10.3762/bjoc.16.166

• endpoint. However, Nicolaou’s route is the shortest (6 or 7 steps, 9.8–9.2% yield), while Kitahara’s synthesis is the highest-yielding and does not involve the use of expensive transition metals or organocatalysts. Syntheses to generate the C-14 stereocenter via C–N bond formation Two groups implemented

Metal-free synthesis of phosphinoylchroman-4-ones via a radical phosphinoylation–cyclization cascade mediated by K₂S₂O₈

• Qiang Liu,
• Weibang Lu,
• Guanqun Xie and
• Xiaoxia Wang

Beilstein J. Org. Chem. 2020, 16, 1974–1982, doi:10.3762/bjoc.16.164

• well-known for their medicinal, biological, or specific material-related properties and have found wide applications in pharmaceutical chemistry, biochemistry, and materials science [21][22][23][24][25][26]. They represent also excellent ligands for many metals and have been used in catalytic systems