Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

• Ritu Mamgain,
• Kokila Sakthivel and
• Fateh V. Singh

Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243

• or without the use of transition metals [44]. Thus, they address both the financial and environmental challenges associated with organic synthesis by acting as environmentally benign substitutes for costly organometallic catalysts and heavy-metal-based oxidants. Diaryl iodide salts consist of two

• significant as it circumvents the use of costly and hazardous metals and ligands which are commercially not available. In order to obtain a variety of synthetically desirable tetrasubstituted α-aryl-α-fluoroacetoacetamides 7, Zaheer et al. disclosed a straightforward, metal-free technique for the α-arylation

• group of the iodonium salt was also investigated. A potential radical-mediated mechanism was evaluated. Under mild conditions, a base-promoted arylation of general sulfinates 86 without the need for transition metals was introduced using diaryliodonium salts 16 as an aryl source (Scheme 35). Inspired by

C–C Coupling in sterically demanding porphyrin environments

• Liam Cribbin,
• Brendan Twamley,
• Nicolae Buga,
• John E. O’ Brien,
• Raphael Bühler,
• Roland A. Fischer and
• Mathias O. Senge

Beilstein J. Org. Chem. 2024, 20, 2784–2798, doi:10.3762/bjoc.20.234

• from the Ni(II)...Ni(II) vector approximately perpendicular to the metals through the c-axis. Upon co-crystallization of borylated porphyrin 46 and bis(pinacolato)diboron, the accommodation of bis(pinacolato)diboron in the void of the lattice was observed (Figure 4). The crystal packing of this

Transition-metal-free decarbonylation–oxidation of 3-arylbenzofuran-2(3H)-ones: access to 2-hydroxybenzophenones

• Bhaskar B. Dhotare,
• Seema V. Kanojia,
• Chahna K. Sakhiya,
• Amey Wadawale and
• Dibakar Goswami

Beilstein J. Org. Chem. 2024, 20, 2655–2667, doi:10.3762/bjoc.20.223

• rearrangement of 2-aryloxybenzaldehydes yielded 2-hydroxybenzophenone [12]. Pd-catalyzed o-hydroxylation of benzophenones gave moderate yield of the title compound, and Br-substituted substrates were found to be not compatible with this method [13]. Various metals (Rh, Cu, Ir etc.) were applied to catalyze the

• oxidative coupling of salicylaldehyde with arylboronic acids to successfully produce 2-hydroxybenzophenones [14]. Recently, a Ni-catalyzed decarbonylation–oxidation of 3-arylbenzofuran-2(3H)-ones emerged as an innovative route to access 2-hydroxybenzophenones [2]. The use of transition metals poses

A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis

• Nian Li,
• Ruzal Sitdikov,
• Ajit Prabhakar Kale,
• Joost Steverlynck,
• Bo Li and
• Magnus Rueping

Beilstein J. Org. Chem. 2024, 20, 2500–2566, doi:10.3762/bjoc.20.214

• industrial settings. An anodic oxidation is frequently employed for C–H functionalization, which can simplify late-stage functionalization strategies. Additionally, many of these synthetic methods do not require precious metals, enhancing their appeal in terms of sustainability and cost-effectiveness

Facile preparation of fluorine-containing 2,3-epoxypropanoates and their epoxy ring-opening reactions with various nucleophiles

• Yutaro Miyashita,
• Sae Someya,
• Tomoko Kawasaki-Takasuka,
• Tomohiro Agou and
• Takashi Yamazaki

Beilstein J. Org. Chem. 2024, 20, 2421–2433, doi:10.3762/bjoc.20.206

• intramolecular interaction between fluorine and metals would also facilitate the smooth progress of these reactions. Such high potential of 1a allowed us to apply it to nucleophilic epoxidation because the resultant epoxyester 2a is recognized as an intriguing building block (Scheme 1). Another expectation to 2a

Electrochemical allylations in a deep eutectic solvent

• Sophia Taylor and
• Scott T. Handy

Beilstein J. Org. Chem. 2024, 20, 2217–2224, doi:10.3762/bjoc.20.189

• spectroscopy to determine that the deposited metal was tin, with traces of other metals consistent with the purity of the initial tin source. The tin recovery was 99% of the theoretical. To explore recycling of this recovered tin, 1 mmol was used in a 0.5 mmol scale allylation of anisaldehyde under the

1,2-Difluoroethylene (HFO-1132): synthesis and chemistry

• Liubov V. Sokolenko,
• Taras M. Sokolenko and
• Yurii L. Yagupolskii

Beilstein J. Org. Chem. 2024, 20, 1955–1966, doi:10.3762/bjoc.20.171

• catalyst (Pd, Pd, Pt, Rh, Ru, Ir, Ni/Cu, Ag, Au, Zn, Cr, Co, Scheme 5) [62][63]. Further, 1,2-Dichloroethylene was reacted with hydrogen fluoride in the presence of metal fluorides or transition metals (Cr, Al, Co, Mn, Ni, Fe) to form 1,2-difluoroethylene (Scheme 6) [56][58]. In patents [59][60], an exotic

Oxidation of benzylic alcohols to carbonyls using N-heterocyclic stabilized λ³-iodanes

• Thomas J. Kuczmera,
• Pim Puylaert and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2024, 20, 1677–1683, doi:10.3762/bjoc.20.149

• easily overoxidized to carboxylic acids. Over the past decades a variety of methods have been developed, utilizing toxic heavy metals such as pyridinium dichromate (PDC) [3][4][5] or manganese dioxide (Figure 1) [6][7]. Molecular oxygen [8] and peroxides [9][10] can also be used as inexpensive terminal

Divergent role of PIDA and PIFA in the AlX₃ (X = Cl, Br) halogenation of 2-naphthol: a mechanistic study

• Kevin A. Juárez-Ornelas,
• Manuel Solís-Hernández,
• Pedro Navarro-Santos,
• J. Oscar C. Jiménez-Halla and
• César R. Solorio-Alvarado

Beilstein J. Org. Chem. 2024, 20, 1580–1589, doi:10.3762/bjoc.20.141

• reactivity [9] usually associated with transition metals [10][11]. Iodine(III) compounds have been used for the formation of different bond types, such as C–C [12][13], C–O [14][15], C–N [16], C–S [17], C–CN [18], C–F [19][20][21], C–I [22][23], C–NO2 [24][25] and, in the context of this work, C–X (X = Cl

Rapid construction of tricyclic tetrahydrocyclopenta[4,5]pyrrolo[2,3-b]pyridine via isocyanide-based multicomponent reaction

• Xiu-Yu Chen,
• Ying Han,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2024, 20, 1436–1443, doi:10.3762/bjoc.20.126

• carbon atom of isocyanide has both a lone electron pair and empty orbitals, so it has outstanding electrophilic and nucleophilic reactivity. At the same time, isocyanide also has good coordination ability to coordinate with metals to form diverse metal complexes [1][2][3]. Therefore, isocyanides have

Diameter-selective extraction of single-walled carbon nanotubes by interlocking with Cu-tethered square nanobrackets

• Guoqing Cheng and
• Naoki Komatsu

Beilstein J. Org. Chem. 2024, 20, 1298–1307, doi:10.3762/bjoc.20.113

• can calculate larger system (>500 atoms) containing transition metals more precisely [16][17]. Result and Discussion Synthesis of Cu-tethered square nanobrackets 1b A pyrene-based nanobracket 4b was synthesized via a one-pot Suzuki coupling followed by the formation of dipyrrin from the dialdehyde 3

Oxidative hydrolysis of aliphatic bromoalkenes: scope study and reactivity insights

• Amol P. Jadhav and
• Claude Y. Legault

Beilstein J. Org. Chem. 2024, 20, 1286–1291, doi:10.3762/bjoc.20.111

• metals, inspired by Nature's metalloproteins. However, using toxic and expensive metals is not always practical, making alternative oxidative methodologies more appealing. Enter hypervalent iodine reagents – a leading metal-free choice for oxidation reactions. These robust and low-toxicity reagents have

Mechanistic investigations of polyaza[7]helicene in photoredox and energy transfer catalysis

• Johannes Rocker,
• Till J. B. Zähringer,
• Matthias Schmitz,
• Till Opatz and
• Christoph Kerzig

Beilstein J. Org. Chem. 2024, 20, 1236–1245, doi:10.3762/bjoc.20.106

• recent years was pioneered by the introduction of photocatalysts (PC) based on metals such as Ru and Ir [1][2][3][4][5][6]. However, due to the high cost and limited availability of precious metals, organic photocatalysts have become a focal point of academic and industrial research [7][8][9][10][11][12

Bismuth(III) triflate: an economical and environmentally friendly catalyst for the Nazarov reaction

• Manoel T. Rodrigues Jr.,
• Aline S. B. de Oliveira,
• Ralph C. Gomes,
• Amanda Soares Hirata,
• Lucas A. Zeoly,
• Hugo Santos,
• João Arantes,
• Catarina Sofia Mateus Reis-Silva,
• João Agostinho Machado-Neto,
• Leticia Veras Costa-Lotufo and
• Fernando Coelho

Beilstein J. Org. Chem. 2024, 20, 1167–1178, doi:10.3762/bjoc.20.99

• heavy metals, the use of bismuth compounds to promote reactions has the advantages of low cost and insensitivity to water and air. As such, the handling does not require special experimental techniques, such as an inert atmosphere and anhydrous solvents [55]. The use of bismuth salts in organic

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

• achieving both selective dehydrogenation and hydrogenation is highly important. A typical BH process is demonstrated in Scheme 1. Several precious transition-metal catalysts have been used successfully in this area, including iridium, rhodium, ruthenium, and osmium [4]. However, these noble metals are toxic

• , expensive, and limited in availability. Hence, replacing them with the first row of transition metals would increase the sustainability and profitability of this procedure [13]. Indeed, many 3d-metal-based homogeneous catalysts have been documented for BH reactions [14][15] since these metals are

• considerably inexpensive, eco-friendly and more abundant in the Earth’s crust. According to this viewpoint, manganese is biocompatible and less expensive than noble metals. Also, it is the third most abundant transition metal, behind titanium and iron. After the independent pioneering works of Beller [16] and

Methodology for awakening the potential secondary metabolic capacity in actinomycetes

• Shun Saito and
• Midori A. Arai

Beilstein J. Org. Chem. 2024, 20, 753–766, doi:10.3762/bjoc.20.69

• compound obtained using approaches for activating silent genes, Wang et al. discovered SF2768, a metabolite produced by Streptomyces thioluteus that chelates copper as a chalkophore [63]. However, it has been suggested that activation of secondary metabolism in actinomycetes may depend on various metals

• . Indeed, it has been reported that adding to the culture medium rare metals not normally used as medium components can activate secondary metabolite biosynthetic genes. For example, Kamijo et al. found that Streptomyces sp. YB-1 produced reddish-purple pigment(s) only in the presence of a rare earth metal

• , ytterbium (Yb), but not in the presence of other metals. Structural analyses revealed that this pigment is a type of naphthoquinone similar to nanaomycin (24) [64]. Furthermore, Tanaka et al. showed that low concentrations of the rare earth elements scandium (Sc) and/or lanthanum (La) markedly activate (2.5

Green and sustainable approaches for the Friedel–Crafts reaction between aldehydes and indoles

• Periklis X. Kolagkis,
• Eirini M. Galathri and
• Christoforos G. Kokotos

Beilstein J. Org. Chem. 2024, 20, 379–426, doi:10.3762/bjoc.20.36

• to the employment of GO–CuBr without overshadowing its applications [113]. Shirini et al. utilized the polymer poly(4-vinylpyridine) (P4VPy) for the immobilization of nanoparticles in lieu of silica, due to the strong affinity of the pyridyl group towards metals and its ability to undergo hydrogen

Chiral phosphoric acid-catalyzed transfer hydrogenation of 3,3-difluoro-3H-indoles

• Yumei Wang,
• Guangzhu Wang,
• Yanping Zhu and
• Kaiwu Dong

Beilstein J. Org. Chem. 2024, 20, 205–211, doi:10.3762/bjoc.20.20

• -catalyzed asymmetric hydrogenation of indoles to synthesize chiral indolines has been widely studied (Scheme 1a) [21][22]. Representative examples include Ir- or Ru-catalyzed asymmetric hydrogenation of 2,3,3-trisubstituted 3H-indole [23][24]. Generally, these methods employ precious metals and/or

Metal-catalyzed coupling/carbonylative cyclizations for accessing dibenzodiazepinones: an expedient route to clozapine and other drugs

• Amina Moutayakine and
• Anthony J. Burke

Beilstein J. Org. Chem. 2024, 20, 193–204, doi:10.3762/bjoc.20.19

• relevant heterocycles in high efficiency [10]. The Chan–Lam coupling is considered a greener alternative to traditional C–N coupling reactions, as it can be carried out under mild reaction conditions (room temperature and short reaction times, etc.), plus it does not require expensive metals like Pd, being

Visible-light-induced radical cascade cyclization: a catalyst-free synthetic approach to trifluoromethylated heterocycles

• Chuan Yang,
• Wei Shi,
• Jian Tian,
• Lin Guo,
• Yating Zhao and
• Wujiong Xia

Beilstein J. Org. Chem. 2024, 20, 118–124, doi:10.3762/bjoc.20.12

• to furnish trifluoromethylated dihyropyrido[1,2-a]indolones under mild conditions, without the need of photocatalysts or transition metals [28]. Results and Discussion We initialized our study by employing Ru(bpy)3Cl2·6H2O and Umemoto’s reagent to generate trifluoromethyl radicals via a photo

Cycloaddition reactions of heterocyclic azides with 2-cyanoacetamidines as a new route to C,N-diheteroarylcarbamidines

• Pavel S. Silaichev,
• Tetyana V. Beryozkina,
• Vsevolod V. Melekhin,
• Valeriy O. Filimonov,
• Andrey N. Maslivets,
• Vladimir G. Ilkin,
• Wim Dehaen and
• Vasiliy A. Bakulev

Beilstein J. Org. Chem. 2024, 20, 17–24, doi:10.3762/bjoc.20.3

• ., Yekaterinburg 620002, Russia Innovation Center for Chemical and Pharmaceutical Technologies, Ural Federal University, 19 Mira st., Yekaterinburg 620002, Russia Department of Medical Biology and Genetics, Ural State Medical University, 3 Repina st., Yekaterinburg 620028, Russian Sustainable Chemistry for Metals

1-Butyl-3-methylimidazolium tetrafluoroborate as suitable solvent for BF₃: the case of alkyne hydration. Chemistry vs electrochemistry

• Marta David,
• Elisa Galli,
• Richard C. D. Brown,
• Marta Feroci,
• Fabrizio Vetica and
• Martina Bortolami

Beilstein J. Org. Chem. 2023, 19, 1966–1981, doi:10.3762/bjoc.19.147

• ], Pd(II) [31][32][33], Pt(II) [34][35], Fe(III) [36][37], Cu(I) [38][39][40][41], Co(III) [42][43][44], as well as other metals, have been widely studied. In addition, methods involving Brønsted acids, alone or in presence of Lewis acids as co-catalysts, have been developed [45][46][47][48][49][50][51

Aldiminium and 1,2,3-triazolium dithiocarboxylate zwitterions derived from cyclic (alkyl)(amino) and mesoionic carbenes

• Nedra Touj,
• François Mazars,
• Guillermo Zaragoza and
• Lionel Delaude

Beilstein J. Org. Chem. 2023, 19, 1947–1956, doi:10.3762/bjoc.19.145

• -dithiocarboxylate zwitterions (Figure 2) [30][31][32][33][34][35][36][37][38][39][40][41][42][43]. These 1,1-dithiolate inner salts strongly bind main group elements and transition metals through various coordination modes. Indeed, we and others have already reported the synthesis of diverse metallic complexes

• metals. Details of these studies will be disclosed in a forthcoming publication. Various types of stable singlet carbenes and their acronyms. Various types of NHC·CS2 zwitterions and their coordination modes. ORTEP representations of zwitterions 4a (CAAC-Mes-Cy·CS2, top) and 4c (CAAC-Die-MePh·CS2, bottom

Beyond n-dopants for organic semiconductors: use of bibenzo[d]imidazoles in UV-promoted dehalogenation reactions of organic halides

• Kan Tang,
• Megan R. Brown,
• Chad Risko,
• Melissa K. Gish,
• Garry Rumbles,
• Phuc H. Pham,
• Oana R. Luca,
• Stephen Barlow and
• Seth R. Marder

Beilstein J. Org. Chem. 2023, 19, 1912–1922, doi:10.3762/bjoc.19.142

• achieved using highly reducing metals, molecular reductants can potentially enable more selectivity, as required for the use of such reactions in the synthesis of molecules bearing various functional groups. In particular, Wanzlick dimers (C=C-bonded dimers of N-heterocyclic carbenes, Figure 1a, i) have

• electropositive metals and may be of use in more elaborate chemical transformations. Mechanism of dark reactions Doping of organic semiconductors by (Y-DMBI)2 dimers [18][39] or by various dimers formed by 18-electron sandwich compounds [18][40][41], as well as redox reactions of other dimers formed by organic

Biphenylene-containing polycyclic conjugated compounds

• Cagatay Dengiz

Beilstein J. Org. Chem. 2023, 19, 1895–1911, doi:10.3762/bjoc.19.141

• naphthazarin and triptycene units (Scheme 14) [48]. Naphthazarin derivatives are known to complex with boron moieties and metals to form electron-poor acene units. Through the Diels–Alder reaction involving dienophile 66, which was formed via the tautomerization of compound 65, and diene 67, compound 68 was