Advancements in hydrochlorination of alkenes

• Daniel S. Müller

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

• state thereof, denoted with an asterisk, possessing a reduction potential of 2.0 V versus SCE (saturated calomel electrode). Subsequently, this excited state undergoes quenching through photoinduced electron transfer (PET) with styrene 5. The resulting vinyl radical cation exhibits electrophilicity at

Synthesis and characterization of water-soluble C₆₀–peptide conjugates

• Yue Ma,
• Lorenzo Persi and
• Yoko Yamakoshi

Beilstein J. Org. Chem. 2024, 20, 777–786, doi:10.3762/bjoc.20.71

• photodynamic therapy photosensitizers (PDT PSs) [41] and magnetic resonance imaging contrast agents (MRI CAs) [42], which are the most relevant topics in fullerene biological studies. Aggregated fullerenes in the micelle structure may cause self-quenching of the excited state of PS fullerenes or may inhibit

SOMOphilic alkyne vs radical-polar crossover approaches: The full story of the azido-alkynylation of alkenes

• Julien Borrel and
• Jerome Waser

Beilstein J. Org. Chem. 2024, 20, 701–713, doi:10.3762/bjoc.20.64

• since the formation of a stabilized carbocation might be required for the reaction to occur. Xu [41] and Molander [42] previously reported the quenching of similar cationic species by alkynyl-BF3K salts. Boronate 5a was therefore selected as nucleophilic alkyne. Gratifyingly, using Cu(dap)2Cl in DCE

Switchable molecular tweezers: design and applications

• Pablo Msellem,
• Maksym Dekthiarenko,
• Nihal Hadj Seyd and
• Guillaume Vives

Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45

• the two metallic centers in the tweezers cavity in a bridging mode. For the heterometallic Zn/Au system, luminescence quenching was observed in the closed state. The pyridine-hydrazine-pyridine unit has been extensively studied by Lehn and co-workers in coordination-responsive supramolecular polymers

• reversibly reopened by the addition of TREN as a competitive ligand. The authors reported a slight luminescence quenching in the zinc-closed state with a decrease in the quantum yield from 0.27 to 0.21. However, Hg2+ presented a special behavior with the formation of a 2:1 complex, the closing of the

• tweezers by the first equivalent generating an allosteric binding site specific to a second Hg2+ ion. While the addition of one equivalent of Hg2+ decreased the quantum yield to 0.09, the formation of a bis-coordinated [tweezers-Hg2]4+ complex resulted in a total luminescence quenching (quantum yield <10−3

Mechanisms for radical reactions initiating from N-hydroxyphthalimide esters

• Carlos R. Azpilcueta-Nicolas and
• Jean-Philip Lumb

Beilstein J. Org. Chem. 2024, 20, 346–378, doi:10.3762/bjoc.20.35

• absorption of light, an excited photocatalyst (*PC) engages in single-electron transfer (SET) with either donor (D) or acceptor (A) molecules (Scheme 3) [8][36]. Accordingly, a reductive quenching mechanism (path a) will operate when an excited photocatalyst effects the one-electron oxidation of a

• sacrificial donor giving rise to a strongly reducing catalytic species (PCn−1). On the other hand, in an oxidative quenching mechanism (path b) the excited photocatalyst directly induces the one-electron reduction of an acceptor substrate. Alternatively, the photocatalyst can mediate the formation of an

• specific activation mechanism, both net reductive and redox neutral transformations can be implemented. Photocatalytic reductive quenching mechanism Among the most common reactions of NHPI esters are radical additions to electron-deficient olefins under net-reductive conditions, often referred to as Giese

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

• reducing agent, O-extrusion takes place with concomitant ring contraction to give the corresponding PBI 6f, isolated in 63% yield after oxidative quenching and work-up. Contrary to photo- or thermal activation, it is important to note that the mechanism for O-extrusion involves in this case the dianion of

Photochromic derivatives of indigo: historical overview of development, challenges and applications

• Gökhan Kaplan,
• Zeynel Seferoğlu and
• Daria V. Berdnikova

Beilstein J. Org. Chem. 2024, 20, 228–242, doi:10.3762/bjoc.20.23

• be assigned to a triplet state was also observed for rigid molecules 10 and 16, based on the quenching experiments and the fact that the same transient species could be found under sensitized conditions. Further insight in the excited state properties of derivatives 9a, 9d, 9g, 9h and N,N

Synthesis of the 3’-O-sulfated TF antigen with a TEG-N₃ linker for glycodendrimersomes preparation to study lectin binding

• Mark Reihill,
• Hanyue Ma,
• Dennis Bengtsson and
• Stefan Oscarson

Beilstein J. Org. Chem. 2024, 20, 173–180, doi:10.3762/bjoc.20.17

• silica gel 60 F254. Visualisation was performed with UV-light (254 nm) fluorescence quenching, and/or by staining with an 8% H2SO4 dip (stock solution: 8 mL conc. H2SO4, 92 mL EtOH), ninhydrin dip (stock solution: 0.3 g ninhydrin, 3 mL AcOH, 100 mL EtOH) and/or ceric ammonium molybdate dip (stock

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

• Michio Yamada

Beilstein J. Org. Chem. 2024, 20, 125–154, doi:10.3762/bjoc.20.13

• emission increases when they are excited at 420 nm, resulting in white-light emission. The underlying mechanism governing these luminescence properties remains unknown. It has been established that 75 does not exhibit luminescence in its solid-state form, which is attributed to the quenching effects

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

• efficient fluorescence quenching (Figure 5), which is commonly observed with this class of cationic ligands [3][70], mainly as a result of a photoinduced electron transfer from the excited, DNA-bound ligand with the DNA bases [71]. The binding isotherms obtained from the titration data were used to

• decrease of the cleavage to 17%. It has to be noted, however, that an inhibition of DNA cleavage in the presence of NaN3 may also be induced by direct deactivation of the excited photosensitizer by the azide and not only from quenching of singlet oxygen [83]. Similar, seemingly contradictory effects of D2O

Aromatic systems with two and three pyridine-2,6-dicarbazolyl-3,5-dicarbonitrile fragments as electron-transporting organic semiconductors exhibiting long-lived emissions

• Karolis Leitonas,
• Brigita Vigante,
• Dmytro Volyniuk,
• Audrius Bucinskas,
• Pavels Dimitrijevs,
• Sindija Lapcinska,
• Pavel Arsenyan and
• Juozas Vidas Grazulevicius

Beilstein J. Org. Chem. 2023, 19, 1867–1880, doi:10.3762/bjoc.19.139

• solutions of compounds 6–9 is increased after deoxygenation by argon (Figure 3a and Figure S2a in Supporting Information File 1). The increase of PL intensity is attributed to a delayed fluorescence turn-on when the triplet quenching by oxygen is omitted. This delayed fluorescence is TADF in nature as it is

Selectivity control towards CO versus H₂ for photo-driven CO₂ reduction with a novel Co(II) catalyst

• Lisa-Lou Gracia,
• Philip Henkel,
• Olaf Fuhr and
• Claudia Bizzarri

Beilstein J. Org. Chem. 2023, 19, 1766–1775, doi:10.3762/bjoc.19.129

• (helping in the deprotonation of the radical cation BIH•+ formed after the reductive quenching of the PS), but also can actively assist the catalysis, by capturing CO2 [50][51][52]. On the other hand, having three hydroxy groups, TEOA is also considered a proton donor and the formation of metal hydrides is

• maximum. Being the emission of [Cu(dmp)DPEPhos](BF4) in DMA/TEA 7:1 567 nm, the value of E00 is 2.19 eV. It follows that Eox* is −1.22 V and Ered* is 0.52 V (see Table S3 in Supporting Information File 1). Thermodynamically, an oxidative quenching of PS* by the catalyst 1 is not feasible (ΔG > 0.3 V

• ), while a reductive quenching by BIH could be possible since the oxidation potential of BIH is 0.27 V (ΔG < −0.25 V). We performed Stern–Volmer analyses to verify our hypothesis. As expected, the lifetime of the PS* (τ0 = 14 ns in aerated DMA/TEA 7:1), is reduced upon the addition of the sacrificial

Charge carrier transport in perylene-based and pyrene-based columnar liquid crystals

• Alessandro L. Alves,
• Simone V. Bernardino,
• Carlos H. Stadtlober,
• Edivandro Girotto,
• Giliandro Farias,
• Rodney M. do Nascimento,
• Sergio F. Curcio,
• Thiago Cazati,
• Marta E. R. Dotto,
• Juliana Eccher,
• Leonardo N. Furini,
• Hugo Gallardo,
• Harald Bock and
• Ivan H. Bechtold

Beilstein J. Org. Chem. 2023, 19, 1755–1765, doi:10.3762/bjoc.19.128

• -shifted in the film. These results indicate molecular π-stacking aggregation and excimer formation on the films [2]. The PL in film was obtained as a function of temperature (Figure 4). The observed reduction of the PL intensity on heating is expected for organic semiconductors due to self-quenching

Tying a knot between crown ethers and porphyrins

• Maksym Matviyishyn and
• Bartosz Szyszko

Beilstein J. Org. Chem. 2023, 19, 1630–1650, doi:10.3762/bjoc.19.120

• alkylammonium guests. The binding constants Ka in CHCl3/MeOH 9:1 determined for 9-Zn complexes with [NH3(CH2)NH2]+, [NH3(CH2)2NH3]2+, [NH3(CH2)3NH3]2+, and [NH3CH2CH3]+ equal to 8.3·103, 6.2·103, 8.7·103, and 7.7·102 M−1, respectively, were reported. Based on the fluorescence quenching experiments the formation

• of coordination compounds of copper(II), iron(II/III), manganese(II), nickel(II), and cobalt(II) with 9-Zn and 9-Cu was demonstrated. The emission quenching was rationalised considering the binding of the transition metal within the crown ether cavity. No quenching was observed upon the addition of

Radical chemistry in polymer science: an overview and recent advances

• Zixiao Wang,
• Feichen Cui,
• Yang Sui and
• Jiajun Yan

Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116

• necessary. MF-ROMP, also termed photo-ROMP, is a novel technique to polymerize cyclic olefins. It begins with the reductive quenching of an photoexcited photocatalyst (PC) at an enol ether initiator to produce a radical cation carrier [90]. Then, the carrier undergoes cyclic addition with a cyclic olefin

• couplings in PATs. Scheme 10 redrawn from [79]. General thiol-ene photopolymerization process. Scheme 11 redrawn from [81]. (a) Three generations of Grubbs catalysts. (b) Proposed mechanism for photo-ROMP via a reductive quenching pathway and (c, d) chemical structures of the (c) initiators and (d) monomers

Cyclodextrins permeabilize DPPC liposome membranes: a focus on cholesterol content, cyclodextrin type, and concentration

• Ghenwa Nasr,
• Hélène Greige-Gerges,
• Sophie Fourmentin,
• Abdelhamid Elaissari and
• Nathalie Khreich

Beilstein J. Org. Chem. 2023, 19, 1570–1579, doi:10.3762/bjoc.19.115

• formulation, a solution containing only liposomes was used as the blank solution. The membrane permeability study by fluorescence spectroscopy The membrane permeability is commonly evaluated by following the leakage of self-quenching probes such as SRB from liposomes [14]. Indeed, a fluorescence auto

• -quenching effect is observed when SRB is encapsulated at a high concentration inside the liposomes. The recovery of the fluorescence signal is achieved upon the release of the dye from liposomes and its dilution in the external medium. Thus, the effect of CDs on the permeability of liposomal membranes was

Functions of enzyme domains in 2-methylisoborneol biosynthesis and enzymatic synthesis of non-natural analogs

• Binbin Gu,
• Lin-Fu Liang and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2023, 19, 1452–1459, doi:10.3762/bjoc.19.104

• by two sequential cyclisation reactions to A and B, and terminal quenching with water. This hypothesis was confirmed by the discovery of the biosynthetic genes coding for a GPP methyltransferase (GPPMT) and a type I terpene synthase termed 2-methylisoborneol synthase (2MIBS) [23][24]. Interestingly

α-(Aminomethyl)acrylates as acceptors in radical–polar crossover 1,4-additions of dialkylzincs: insights into enolate formation and trapping

• Angel Palillero-Cisneros,
• Paola G. Gordillo-Guerra,
• Fernando García-Alvarez,
• Olivier Jackowski,
• Franck Ferreira,
• Fabrice Chemla,
• Joel L. Terán and
• Alejandro Perez-Luna

Beilstein J. Org. Chem. 2023, 19, 1443–1451, doi:10.3762/bjoc.19.103

• addition (Scheme 7, bottom). Much to our surprise however, no deuterium incorporation is observed on quenching with ND4Cl/D2O the reaction between 8a and Et2Zn. By contrast, a significant deuterium incorporation is obtained when deuterated starting material (8a-d) is engaged. The combination of these two

Organic thermally activated delayed fluorescence material with strained benzoguanidine donor

• Alexander C. Brannan,
• Elvie F. P. Beaumont,
• Nguyen Le Phuoc,
• George F. S. Whitehead,
• Mikko Linnolahti and
• Alexander S. Romanov

Beilstein J. Org. Chem. 2023, 19, 1289–1298, doi:10.3762/bjoc.19.95

• aerated MCH solution. The reduction in quantum yield on exposure to oxygen is due to quenching of the triplet excited states indicating a TADF luminescence mechanism. PLQY in Zeonex films is 39% in air, which is lower than the PLQY of 87% reported for 4CzIPN [17]. The two-component excited state lifetime

Radical ligand transfer: a general strategy for radical functionalization

• David T. Nemoto Jr,
• Kang-Jie Bian,
• Shih-Chieh Kao and
• Julian G. West

Beilstein J. Org. Chem. 2023, 19, 1225–1233, doi:10.3762/bjoc.19.90

• paradigm with photocatalytic ATRA to enable the modular difunctionalization of alkenes under reagent control (Scheme 3). In Stephenson’s photocatalytic ATRA reports, the C–X bond in the product was proposed to be formed through both direct quenching of a transient alkyl radical by halogen atom transfer

Enabling artificial photosynthesis systems with molecular recycling: A review of photo- and electrochemical methods for regenerating organic sacrificial electron donors

• Grace A. Lowe

Beilstein J. Org. Chem. 2023, 19, 1198–1215, doi:10.3762/bjoc.19.88

• in systems for carbon dioxide reduction (see Figure 1). Reductive quenching of the photosensitizer occurs when the sacrificial donor reduces the photoexcited photosensitizer (reductive quenching pathway). Regeneration of photooxidized photosensitizers occurs when the excited dye is first oxidatively

• quenched by a substrate or catalyst and then reduced by the sacrificial donor (oxidative quenching pathway). In the presence of protons, proton donors, or oxidized donor species with a low pKa, a proton-coupled electron transfer (PCET) can take place [14][15]. PCET reactions are important in artificial

• low absorption in the visible region to prevent side reactions and allow the photosensitizer to absorb as much light as possible. The oxidation potential of the sacrificial electron donor must be less positive than the reduction potential of the excited or oxidized photosensitizer for quenching or

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

• intermediates under mild conditions for both oxidative and reductive reactions and ii) to use photons as traceless reagents to drive reactions in a “greener” manner [1][2][3][4][5][6]. As depicted in Figure 1, for an oxidative PRC cycle, the excited photocatalyst (*PC) firstly undergoes oxidative quenching by

• ). In a complementary manner, *PC generates A•− and D•+ within a reductive quenching cycle via SET reactions. The milder conditions that PRC enjoys to access potent redox agents guarantees sustainable and safer processes when compared to classical methods of equivalent redox power. For example, in the

• while the C(sp2)–Br bond remained untouched. Subsequent irradiation with blue light gave the sequentially substituted products 9c and 9d. As with PDI, the xanthene dye rhodamine 6G (Rh-6G) can undergo reductive quenching upon excitation with green or blue light (Figure 5C). Considering that Rh-6G

The effect of dark states on the intersystem crossing and thermally activated delayed fluorescence of naphthalimide-phenothiazine dyads

• Liyuan Cao,
• Xi Liu,
• Xue Zhang,
• Jianzhang Zhao,
• Fabiao Yu and
• Yan Wan

Beilstein J. Org. Chem. 2023, 19, 1028–1046, doi:10.3762/bjoc.19.79

• infer that the emissive S1 state has a substantial CS character [56]. Thus, the assignment of the emissive S1 state to a CS state is reasonable. Upon oxidation of the PTZ moiety, the degree of fluorescence quenching in polar solvents became less significant than that of the compounds with a native PTZ

• fluorescence under nitrogen atmosphere and a substantial quenching under air or oxygen atmosphere [22], the fluorescence spectra of the dyads containing native PTZ unit under different atmospheres were studied (Figure 3a–d and Figure S32a in Supporting Information File 1). The results show that the

• Supporting Information File 1), the fluorescence intensity is less dependent on the atmosphere. Moreover, we suggest that the reduced luminescence of the oxidized molecules in air may be caused by the quenching effect of oxygen to the S1 state. According to this experimental phenomenon, we preliminarily

Linker, loading, and reaction scale influence automated glycan assembly

• Marlene C. S. Dal Colle,
• Manuel G. Ricardo,
• Nives Hribernik,
• José Danglad-Flores,
• Peter H. Seeberger and
• Martina Delbianco

Beilstein J. Org. Chem. 2023, 19, 1015–1020, doi:10.3762/bjoc.19.77

• some peptide sequences [18]. Moreover, high-loading supports might result in inefficient UV cleavage due to quenching. These four supports were studied in AGA experiments performed at 15 and 30 µmol reaction scales. While AGA is commonly performed at a 15 µmol reaction scale, a larger reaction scale is

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

• easily generate reactive open-shell radical species and/or intermediates. The substrate is consequently activated for bond cleavage, atom abstraction, or nucleophilic or electrophilic attack. After quenching, the oxidized or reduced photocatalyst regains or loses an electron to return to the starting