Auxiliary strategy for the general and practical synthesis of diaryliodonium(III) salts with diverse organocarboxylate counterions

• Naoki Miyamoto,
• Daichi Koseki,
• Kohei Sumida,
• Elghareeb E. Elboray,
• Naoko Takenaga,
• Ravi Kumar and
• Toshifumi Dohi

Beilstein J. Org. Chem. 2024, 20, 1020–1028, doi:10.3762/bjoc.20.90

• a cartridge filled with powdered oxone® for in situ generation of bis(trifluoroacetoxyiodo)arenes and their reaction with electron-rich arene or arylboronic acid [19] (Scheme 1B). Carboxylic acids, such as acetic acid and benzoic acid, characterized by substantial difference in pKa values when

Advancements in hydrochlorination of alkenes

• Daniel S. Müller

Beilstein J. Org. Chem. 2024, 20, 787–814, doi:10.3762/bjoc.20.72

• (anti-Markovnikov product). One plausible explanation for this intriguing observation is that K10 and other zeolites may function both as Brønsted acids and radical initiators [63]. Consequently, it is likely that both ionic and radical pathways are concurrently in operation. The in situ generation of

• . Formation of chlorophosphonium complex 104 and the reaction thereof with H2O. Snyder’s hydrochlorination with stoichiometric amounts of complex 104 or 108. In situ generation of HCl by mixing of MsOH with CaCl2. First hydrochlorination of alkenes using hydrochloric acid. Visible-light-promoted

Ligand effects, solvent cooperation, and large kinetic solvent deuterium isotope effects in gold(I)-catalyzed intramolecular alkene hydroamination

• Ruichen Lan,
• Brock Yager,
• Yoonsun Jee,
• Cynthia S. Day and
• Amanda C. Jones

Beilstein J. Org. Chem. 2024, 20, 479–496, doi:10.3762/bjoc.20.43

• exchange (t < 5 minutes) reduced the N–CH2 doublet (δ 3.84 ppm in CD2Cl2) to a singlet, indicating high incorporation of deuterium into the substrate and corresponding in situ generation of CH3OH. Furthermore, both NH signals appear absent in the 1H NMR spectrum (δ 3.93/3.66). Comparing the rates of

Synthesis of π-conjugated polycyclic compounds by late-stage extrusion of chalcogen fragments

• Aissam Okba,
• Pablo Simón Marqués,
• Kyohei Matsuo,
• Naoki Aratani,
• Hiroko Yamada,
• Gwénaël Rapenne and
• Claire Kammerer

Beilstein J. Org. Chem. 2024, 20, 287–305, doi:10.3762/bjoc.20.30

• of devices and in situ generation of the active material by late stage S-extrusion. Nevertheless, the synthetic route towards dinaphthothiepine bisimides initially reported suffered from several drawbacks: it had limited efficiency (1.2% overall yield over 8 steps for the synthesis of thiepine 3a

• contraction, accompanied with the extrusion of a chalcogen fragment, have led to the preparation of a variety of π-CPCs, displaying a wide range of 2D or 3D structures. While contraction of 6-membered rings has not been exploited yet for the in situ generation of molecular materials, chalcogen extrusion from

• variety of π-conjugated polycyclic structures upon thermal activation, photoirradiation and redox control. While contraction of 6-membered rings has not been exploited yet for the in situ generation of molecular materials, chalcogen extrusion from group-16 heteropines was successfully implemented as a key

Photoinduced in situ generation of DNA-targeting ligands: DNA-binding and DNA-photodamaging properties of benzo[c]quinolizinium ions

• Julika Schlosser,
• Olga Fedorova,
• Yuri Fedorov and
• Heiko Ihmels

Beilstein J. Org. Chem. 2024, 20, 101–117, doi:10.3762/bjoc.20.11

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

• commercially available BF3 diethyl etherate (BF3·Et2O), commonly used in organic synthesis. Indeed, the main advantages of the developed system are: 1) in situ generation of BF3, which avoids its storage and handling, 2) the possibility to control the amount of electrogenerated BF3 using current by simply

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

• lack of conjugation between the heterocyclic core of the molecules and their peripherical decorations. Conclusion The synthesis of three CAAC·CS2 and six MIC·CS2 zwitterions derived from aldiminium or 1,2,3-triazolium salts was achieved via a two-step procedure involving the in situ generation of free

Application of N-heterocyclic carbene–Cu(I) complexes as catalysts in organic synthesis: a review

• Nosheen Beig,
• Varsha Goyal and
• Raj K. Bansal

Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

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

• and stereoselectivity (Scheme 8) [58]. The mechanism of this reaction differs from the previously reported ones and proceeds through the in situ generation of nucleophilic and electrophilic partners which provides new opportunities for enantioselective oxocarbenium ion-driven CDC processes. Due to an

Retraction: One-pot odourless synthesis of thioesters via in situ generation of thiobenzoic acids using benzoic anhydrides and thiourea

• Mohammad Abbasi and
• Reza Khalifeh

Beilstein J. Org. Chem. 2023, 19, 1170–1170, doi:10.3762/bjoc.19.85

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

• radical. This is strongly supported by a single turnover experiment, where exclusive excitation of [FeII(btz)3]2+ with 700 nm LEDs after in situ generation and substrate addition in the dark generated 5% of product even with only 0.5 mol % of catalyst present. In its ground state, [FeII(btz)3]2+ is not

Copper-catalyzed N-arylation of amines with aryliodonium ylides in water

• Kasturi U. Nabar,
• Bhalchandra M. Bhanage and
• Sudam G. Dawande

Beilstein J. Org. Chem. 2023, 19, 1008–1014, doi:10.3762/bjoc.19.76

• ]. Further, a few reports are also available for the copper and palladium-catalyzed N-arylation of primary and secondary aliphatic as well as aromatic amines using diaryliodonium salts as aryl sources [33][34][35] (Scheme 1a). Similarly, iodonium ylides undergo a wide range of reactions through in situ

• generation of carbene as a reactive intermediate [36][37]. Also, spirocyclic iodonium ylides have been used for radiolabeling techniques [38]. In 2013, Shibata’s research group reported a novel trifluoromethanesulfonyl iodonium ylide for trifluoromethylthiolation of enamines, indoles, and ketoesters

Palladium-catalyzed enantioselective three-component synthesis of α-arylglycine derivatives from glyoxylic acid, sulfonamides and aryltrifluoroborates

• Bastian Jakob,
• Nico Schneider,
• Luca Gengenbach and
• Georg Manolikakes

Beilstein J. Org. Chem. 2023, 19, 719–726, doi:10.3762/bjoc.19.52

• situ generation of reactive imine species, we have disclosed iron- and bismuth-catalyzed three-component reactions for the synthesis of α-arylglycines [14][15][16], in which the arylboronic acid could be replaced with an electron-rich (hetero)arene as nucleophile. In parallel, we have developed

• electrophilic iminium carbon, leading to the amine product as racemic mixture. Consequently, examples for asymmetric Petasis borono-Mannich reactions are rare [13] and usually rely on the utilization of chiral amine components in stoichiometric amounts [10][11]. As part of our research program utilizing the in

A one-pot electrochemical synthesis of 2-aminothiazoles from active methylene ketones and thioureas mediated by NH₄I

• Shang-Feng Yang,
• Pei Li,
• Zi-Lin Fang,
• Sen Liang,
• Hong-Yu Tian,
• Bao-Guo Sun,
• Kun Xu and
• Cheng-Chu Zeng

Beilstein J. Org. Chem. 2022, 18, 1249–1255, doi:10.3762/bjoc.18.130

• the in situ generation of α-iodocarbonyl ketones from constant current electrolysis (CCE) of ketones in the presence of iodide ions. It is worth noting that we have also reported an electrochemical method for the synthesis of 2-aminothiazoles via the one-pot direct α-C–H functionalization of ketones

First series of N-alkylamino peptoid homooligomers: solution phase synthesis and conformational investigation

• Maxime Pypec,
• Laurent Jouffret,
• Claude Taillefumier and
• Olivier Roy

Beilstein J. Org. Chem. 2022, 18, 845–854, doi:10.3762/bjoc.18.85

• situ generation of a mixed anhydride [45]. This method gave the highest coupling yield to dimer 2d, but again with the condition of using an excess of the acid partner, as some of it was consumed to give the byproduct ethyl ester 1e. Dimer 2d was obtained for example in 95% yield from 1.5 equivalents

• isolated in 78% yield after chromatography. The use of stoichiometric amounts of both partners led to incomplete conversion, with about 1/3 of the starting hydrazine being recovered after two days of reaction. We then tested 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ), in dioxane, a method for in

Copper-catalyzed multicomponent reactions for the efficient synthesis of diverse spirotetrahydrocarbazoles

• Shao-Cong Zhan,
• Ren-Jie Fang,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2022, 18, 796–808, doi:10.3762/bjoc.18.80

• '-indolines] 2a–h, in which the two phenyl groups exist in cis-position. This result clearly indicated that this reaction has a similar outcome of stereochemistry. Based on the success of the four-component reaction through in situ generation of dienes and dienophiles, we further considered whether more

• results indicate the in situ generation of both indole-based ortho-quinodimethanes (o-QDMs) as active dienes and cyclic dienophiles are the key intermediates in these reactions. Moreover, this protocol exhibited good functional group tolerance, broad substrate scope and facile scalability. It would

Complementarity of solution and solid state mechanochemical reaction conditions demonstrated by 1,2-debromination of tricyclic imides

• Petar Štrbac and
• Davor Margetić

Beilstein J. Org. Chem. 2022, 18, 746–753, doi:10.3762/bjoc.18.75

• ] could be simplified by in situ generation of the catalyst. Moreover, in the debromination of norbornene imide 11, the expected Diels−Alder adduct with furan was not obtained, but compound 12 incorporating a tetrahydrofuran ring at position 2, presumably by radical reaction (Figure 2) [19][20]. We

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

• coupled with in situ generation of the azide from the corresponding bromide. The 1,2,3-triazoles are formed in up to 99% yield and in less than 10 minutes residence time, which includes azide formation prior to the cycloaddition step. Interestingly, this process could not be successfully repeated under

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

• yield was only 10%, but after the addition of MTO and acetic anhydride, the yield increased to 46% (Table 1, entry 5) [51]. The authors suggested two simultaneous reaction pathways: a direct oxidation by rhenium bisperoxo complex and an MTO-catalyzed in situ generation of peroxyacetic acid as oxidant

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

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

• derivative 99, followed by aromatization under the described conditions. The preliminary in vitro antitumor studies of the compounds displayed low to moderate activity. Scheme 37 depicts the mechanism wherein an initial in situ generation of α,β-unsaturated intermediate A occur due to the Knoevenagel

[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

• voltammetry. One of the approaches for in situ generation of unstable diazo compounds involves the use of stable hydrazones, followed by their oxidation with MnO2. For example, the scientists led by van Koten and co-workers synthesized a group of methanofullerenes with monoanionic terdentate diaminoaryl

Synthesis of imidazo[1,5-a]pyridines via cyclocondensation of 2-(aminomethyl)pyridines with electrophilically activated nitroalkanes

• Dmitrii A. Aksenov,
• Nikolai A. Arutiunov,
• Vladimir V. Maliuga,
• Alexander V. Aksenov and
• Michael Rubin

Beilstein J. Org. Chem. 2020, 16, 2903–2910, doi:10.3762/bjoc.16.239

• approach, however, seems less attractive as it requires an additional step for the proper modification of the starting material. An alternative, more appealing method would capitalize on the in situ generation of a less sterically hindered, and therefore more reactive electrophilic nitronate. As we have

Anion exchange resins in phosphate form as versatile carriers for the reactions catalyzed by nucleoside phosphorylases

• Julia N. Artsemyeva,
• Ekaterina A. Remeeva,
• Tatiana N. Buravskaya,
• Irina D. Konstantinova,
• Roman S. Esipov,
• Anatoly I. Miroshnikov,
• Natalia M. Litvinko and
• Igor A. Mikhailopulo

Beilstein J. Org. Chem. 2020, 16, 2607–2622, doi:10.3762/bjoc.16.212

• of dIno) in 10 mM Na-phosphate buffer (pH 7.4) at 22 °C for 6 h. Noteworthy, the formation of the 2'd-N7- and 2'd-N9-glycosides of N2-acetylguanine (AcGua) was observed in the transglycosylation of AcGua using dGuo/E. coli PNP (67.5 IU per 1 mmol base) for an in situ generation of dRib-1Pi (5 mM K

• reaction of OMG (Ara-U as a donor of Ara-1Pi) and 2-fluoroadenine [1-(β-ᴅ-arabinofuranosyl)cytosine (Ara-C) + cytidine deaminase for an in situ generation of Ara-1Pi], respectively, and the recombinant E. coli UP and PNP as biocatalysts in an one-pot mode. Unexpectedly, a significantly lower efficiency of