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

• under blue light irradiation afforded 4a in 17% NMR yield (Table 2, entry 1). The major byproduct formed during the transformation was identified as diazide 6. When a copper photocatalyst is involved, a lot of diazidation can be observed. We assumed it could be caused by the reaction of Ts-ABZ (3) with

• and 5). Surprisingly, 5a could be used as limiting reagent without impacting the reaction (Table 4, entry 6). Carrying out the azido-alkynylation at low or high photocatalyst loading had no impact (Table 4, entry 7). Considering the robustness of the reaction to fluctuation in stoichiometry

• mixture was obtained due to the presence of the photocatalyst. Further investigation revealed that Ru(bpy)3Cl2·6H2O is not soluble in DME (Scheme 2B). In contrast, when it is in the presence of alkynyl-BF3K it readily dissolves. The addition of a couple of water drops to a suspension of photocatalyst in

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

• type addition reactions (Scheme 4A). In 1991, Okada and co-workers reported the addition of alkyl radicals to α,β-unsaturated ketones, by subjecting NHPI esters to visible-light irradiation in the presence of the photocatalyst [Ru(bpy)3]Cl2 and the reductant 1-benzyl-1,4-dihydronicotinamide (BNAH) [37

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

• that omitting the photocatalyst led to an even higher yield (Table 1, entry 2), but light irradiation was essential to the reaction (Table 1, entries 3 and 4). Initially, some bases were added into the reaction system considering a deprotonation process, but subsequent investigations indicated that

Optimizing reaction conditions for the light-driven hydrogen evolution in a loop photoreactor

• Pengcheng Li,
• Daniel Kowalczyk,
• Johannes Liessem,
• Mohamed M. Elnagar,
• Dariusz Mitoraj,
• Radim Beranek and
• Dirk Ziegenbalg

Beilstein J. Org. Chem. 2024, 20, 74–91, doi:10.3762/bjoc.20.9

• evolution using a Pt-loaded polymeric carbon nitride photocatalyst under 365 nm irradiation in the presence of sacrificial reducing agents. The fluid flow pattern of the developed photoreactor was characterized experimentally and the photon flux incident to the loop photoreactor was measured by chemical

• actinometry. The system displayed exceptional stability, with operation sustained over 70 hours. A design of experiment (DOE) analysis was used to systematically investigate the influence of key parameters – photon flux, photocatalyst loading, stirring speed, and inert gas flow rate – on the hydrogen

• generation rate. Linear relationships were found between hydrogen evolution rate and photon flux as well as inert gas flow rate. Photocatalyst loading and stirring speed also showed linear correlations, but could not be correctly described by DOE analysis. Instead, linear single parameter correlations could

Using the phospha-Michael reaction for making phosphonium phenolate zwitterions

• Matthias R. Steiner,
• Max Schmallegger,
• Larissa Donner,
• Johann A. Hlina,
• Christoph Marschner,
• Judith Baumgartner and
• Christian Slugovc

Beilstein J. Org. Chem. 2024, 20, 41–51, doi:10.3762/bjoc.20.6

• candidates as well. Ortho-hydroxy-substituted phosphines have been mainly used as chelating ligands for metal complexes until recently [16][17][18]. Further, ortho-hydroxy phosphines have been used for the synthesis of probes in metabolic labeling [19], as a photocatalyst in the defluoroalkylation 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

• photooxidation of polystyrene in the presence of FeCl3 as a radical source (Scheme 21a) [202]. A molar yield of 23% benzoyl small molecules was achieved. Reisner and co-workers employed a similar approach but using aromatic ketones as photocatalyst (Scheme 21b) [203]. Benzoic acid and other aromatic small

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

• in functionalizing unactivated C(sp3)–H substrates, including ethers [109][110][111][112][113][114]. In 2018, Wang et al. reported the photocatalytic CDC α-alkylation of N-heteroarenes in acetone solution, using noble-metal Ir as a photocatalyst to induce the reaction (Scheme 41) [115]. Subsequently

• , noble metals have been extensively studied as photocatalysts for CDC reactions [116][117][118][119][120][121] and these methods fill the gap of traditional thermocatalytic CDC reactions. In 2017, Ryu et al. developed tetrabutylammonium decatungstate (TBADT, (n-Bu4N)4[W10O32] as a photocatalyst to

• this type of CDC reaction (Scheme 43b–e). Efficient CDC reactions could be achieved with 1 mol % of eosin Y in the absence of additional base or oxidizing agents. In this transformation, eosin Y may act as a direct hydrogen atom transfer photocatalyst (Scheme 43b) [124]. The CDC reaction between

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

• who used a similar photocatalyst to systematically study ferrocene derivatives as sacrificial donors [31]. The ferrocene derivatives reductively quenched the photosensitizer but could not accumulate as effectively as the BIH derivatives used by Gimeno et al. [29][31]. In contrast, Z-schemes that

• photocatalyst which re-reduced DcMFc and evolved oxygen. The same reaction scheme was used but in a modified H-cell (Figure 2B) [35]. Both catalysts were confined at the ITIES in two separate chambers and the redox mediator diffused between the two cells via the organic phase. The protons for hydrogen evolution

• migrated and diffused via the aqueous layer. The photoelectrochemical recycling was also studied in a system with one ITIES where the photocatalyst was immobilized and water oxidation was carried out at an electrode in the aqueous layer (Figure 2C). This electrode was connected to a counter electrode in

Selective and scalable oxygenation of heteroatoms using the elements of nature: air, water, and light

• Damiano Diprima,
• Hannes Gemoets,
• Stefano Bonciolini and
• Koen Van Aken

Beilstein J. Org. Chem. 2023, 19, 1146–1154, doi:10.3762/bjoc.19.82

• left out in future experiments) and no conversion was observed in the dark experiment. Surprisingly, after removal of the TiO2 photocatalyst from the reaction matrix, still an identical conversion of 10% was achieved. Additionally, replacing the inert atmosphere (argon) with oxygen had a drastic

• positive impact on the reaction outcome. By running the reaction in the presence of oxygen and in the absence of a photocatalyst, a quantitative conversion into the sulfoxide was obtained within 60 minutes in batch (Table 1, entry 1). To shed more light on what could be the absorbing species within the

• photocatalyst. Substrate scope with reaction times and isolated yields. 1 mmol (1 equiv) substrate was reacted in a 5 mL solution of CH3CN/H2O 8:2 (v:v). The reaction mixture was irradiated with a 365 nm 96 W lamp at a distance of 5 cm from the reactor. Oxygen was bubbled through the solution. a10 mL solution

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

• SET with an electron acceptor (A), leading to PC•+ and A•−. The ground state photocatalyst is then regenerated by an SET reaction with an electron donor (D), affording also D•+. Both species described can be further involved in various organic transformations to form the target products (or byproducts

• generation of super-reductants [15] and by Wagenknecht in 2018 for the generation of super-oxidants [16]. Herein, initial excitation of the photocatalyst by a single photon is followed by reduction or oxidation by a sacrificial SET donor (e.g., Et3N [15]) or acceptor (e.g., SF6 [16]) to yield the catalyst

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

• photocatalyst. Keywords: decarboxylative cyclization; DMAT; ergot alkaloids; photoredox catalysis; radicals; Introduction Visible-light photoredox catalysis is rapidly changing the way organic chemists approach the design and synthesis of molecules by offering new synthetic disconnection opportunities that

• 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

• of all ergot alkaloids, specifically the decarboxylative cyclization of DMAT, is still a puzzle even though a radical mechanism has been proposed (Figure 1a) [72][73]. Results and Discussion Herein, we propose that visible light irradiation of the cationic iridium photocatalyst Ir[dF(CF3)ppy]2(dtbbpy

Photocatalytic sequential C–H functionalization expediting acetoxymalonylation of imidazo heterocycles

• Deepak Singh,
• Shyamal Pramanik and
• Soumitra Maity

Beilstein J. Org. Chem. 2023, 19, 666–673, doi:10.3762/bjoc.19.48

• investigation revealed a sequential sp2 and sp3 C–H activation, followed by functionalization driven by zinc acetate coupled with the photocatalyst PTH. A variety of imidazo[1,2-a]pyridines and related heterocycles were explored as substrates along with several active methylene reagents, all generating the

• boron complex (B2pin2), and using an expensive metal-based photocatalyst [fac-Ir(ppy)3] under inert atmosphere. We have recently demonstrated that aerial oxygen could be captured by alkyl radicals to install a keto-functionality onto alkenes in an organophotocatalytic way [23]. We aimed to extend this

• reaction was carried out between 1a and 2a in dry CH3CN as solvent under N2 atmosphere using 4CzIPN as the photocatalyst. Irradiating the reaction mixture for 10 h under blue LEDs (450 nm) led to the isolation of products 5 (54%) and 6 (28%) (Table 1, entry 1). However, the same reaction, under aerobic

Transition-metal-catalyzed domino reactions of strained bicyclic alkenes

• Austin Pounder,
• Eric Neufeld,
• Peter Myler and
• William Tam

Beilstein J. Org. Chem. 2023, 19, 487–540, doi:10.3762/bjoc.19.38

• reactivity with a few examples failing to provide the desired product when 4-CzIPN was used as the photocatalyst; however, the products were isolated when [Ir(dF(CF3)ppy)2(bpy)]PF6 was used. Based on experimental observations and control reactions, the authors proposed the reaction begins with the

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

• lutidine base, 7 mol % organic photocatalyst 4CzIPN, 30 mol % NiBr2, and 30 mol % bpy provided 57% of 9. Intramolecular Friedel–Crafts reaction by Et2AlCl and HFIP complex led to 123, possessing the correct connectivity for the divergent synthesis of the family. Choreographically executed sequential

• ). Thus, upon irradiation, iridium polypyridyl photocatalyst allowed the oxidation of the phosphate complex 207 to radical cation 206, which can be readily trapped by TEMPO, and hence stabilizing the imine and allowing cyclization with the pendant amine to form the pyrroloindoline core 210 in 81% yield

• and 93% ee. The latter can serve as a common scaffold to access an array of pyrroloindoline natural products but also synthetic analogues (Scheme 17). Oxidation of 210 by a second iridium photocatalyst yields benzyl cation 213, which can undergo nucleophilic attack by tryptamine derivatives to allow

Inline purification in continuous flow synthesis – opportunities and challenges

• Jorge García-Lacuna and
• Marcus Baumann

Beilstein J. Org. Chem. 2022, 18, 1720–1740, doi:10.3762/bjoc.18.182

• produced as byproduct in the metathesis reaction. Some subsequent publications include the Pd-complex removal after a Suzuki coupling [126], a Heck catalyst retention with reverse boiling-point-order solvent exchange [127], and a membrane for recovery of the photocatalyst TBADT (tetrabutylammonium

Heterogeneous metallaphotoredox catalysis in a continuous-flow packed-bed reactor

• Wei-Hsin Hsu,
• Susanne Reischauer,
• Peter H. Seeberger,
• Bartholomäus Pieber and
• Dario Cambié

Beilstein J. Org. Chem. 2022, 18, 1123–1130, doi:10.3762/bjoc.18.115

• simultaneous separation of both the photocatalyst and metal-catalyst is achieved. The combination of both catalytic activities in a single material is crucial to obtain this result, as a mixture of a heterogeneous photocatalyst with an immobilized metal catalyst would be problematic both in terms of packed bed

Radical cation Diels–Alder reactions of arylidene cycloalkanes

• Kaii Nakayama,
• Hidehiro Kamiya and
• Yohei Okada

Beilstein J. Org. Chem. 2022, 18, 1100–1106, doi:10.3762/bjoc.18.112

• Information File 96: General remarks, photocatalyst analyzation data, synthesis procedure, additional control studies, electrochemical measurements, and characterization data, including copies of 1H and 13C NMR spectra. Funding This work was supported in part by JSPS KAKENHI grant Nos. 16H06193, 17K19221

Electrochemical Friedel–Crafts-type amidomethylation of arenes by a novel electrochemical oxidation system using a quasi-divided cell and trialkylammonium tetrafluoroborate

• Hisanori Senboku,
• Mizuki Hayama and
• Hidetoshi Matsuno

Beilstein J. Org. Chem. 2022, 18, 1040–1046, doi:10.3762/bjoc.18.105

• -acyliminium ions in chemical methods has been generally accomplished by the reaction of amides with chemical oxidants, such as peroxides and persulfates at high temperature (path a in Scheme 1) [10][11][12][13]. A metal catalyst or a photocatalyst consisting of metals, such as ruthenium or iridium, is also

Heteroleptic metallosupramolecular aggregates/complexation for supramolecular catalysis

• Prodip Howlader and
• Michael Schmittel

Beilstein J. Org. Chem. 2022, 18, 597–630, doi:10.3762/bjoc.18.62

Tetraphenylethylene-embedded pillar[5]arene-based orthogonal self-assembly for efficient photocatalysis in water

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

Beilstein J. Org. Chem. 2022, 18, 429–437, doi:10.3762/bjoc.18.45

• -acetonaphthone (2j, 50%, Figure S13) demonstrating the general applicability of m-TPEWP5G-EsY as an efficient photocatalyst. To understand the process for this photocatalytic dehalogenation reaction, a possible reaction mechanism is proposed in Figure 5 [37]. Upon light irradiation, the ground state of m-TPEWP5G

• UV light. Proposed mechanism for the 2-bromo-1-phenylethanone dehalogenation reaction mediated by m-TPEWP5G-EsY nanoassembly as a photocatalyst. Graphical representation of the fabrication of supramolecular m-TPEWP5G-EsY self-assembled photocatalytic system. Products from 2-bromo-1-phenylethanone

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

Recent advances and perspectives in ruthenium-catalyzed cyanation reactions

• Thaipparambil Aneeja,
• Cheriya Mukkolakkal Abdulla Afsina,
• Padinjare Veetil Saranya and
• Gopinathan Anilkumar

Beilstein J. Org. Chem. 2022, 18, 37–52, doi:10.3762/bjoc.18.4

• 2021. Keywords: cyanation; nitriles; photocatalyst; ruthenium; tertiary amines; Introduction Nitriles are a major class of organic compounds having wide significance in materials science, agrochemical and pharmaceutical industry [1]. They are the privileged compounds finding broad applications in

• oxidative cyanation of aza-Baylis–Hillman adducts. Synthesis of 1° alkyl nitriles using [Ru(bpy)3](PF6)2 as the photocatalyst. Synthesis of 2° and 3° alkyl nitriles using [Ru(bpy)3](PF6)2 as the photocatalyst. Photoredox cross coupling reaction. Synthesis of α-amino nitriles from amines via a one-pot

DABCO-promoted photocatalytic C–H functionalization of aldehydes

• Bruno Maia da Silva Santos,
• Mariana dos Santos Dupim,
• Cauê Paula de Souza,
• Thiago Messias Cardozo and
• Fernanda Gadini Finelli

Beilstein J. Org. Chem. 2021, 17, 2959–2967, doi:10.3762/bjoc.17.205

• -bromobenzonitrile (2) under different amounts of DABCO. Two inorganic bases were tested: potassium carbonate (K2CO3) and sodium hydrogen carbonate (NaHCO3). Reactions in the absence of inorganic bases were also performed (Table 1). An excited iridium photocatalyst (Ir[dF(CF3)ppy]2(dtbbpy)PF6) was used for the one

• and 13), there was a significant improvement in the yield when using NaHCO3 (Table 1, entry 5), even when compared to the results obtained with K2CO3. No product was observed when the reaction was performed in the dark (Table 1, entry 7) or in the absence of the iridium photocatalyst (Table 1, entry 8

• radical hydrogen abstraction may be possible under similar conditions [31][32]. However, even small amounts of DABCO (Table 1, entry 1) seem to completely shut down this alternative path, probably due to a fast quenching of the excited state photocatalyst, leading to no mechanism competition under the

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

Visible-light-mediated copper photocatalysis for organic syntheses

• Yajing Zhang,
• Qian Wang,
• Zongsheng Yan,
• Donglai Ma and
• Yuguang Zheng

Beilstein J. Org. Chem. 2021, 17, 2520–2542, doi:10.3762/bjoc.17.169

• the photocatalyst RuII is irradiated by light, an electron is transferred from the frontier metal d orbital (t2g orbital) to the ligand-centered π* orbital (RuII*). A metal-to-ligand charge transfer (MLCT) results in the excited singlet state. Through rapid intersystem crossing (ISC), the singlet

• thiocyanate to generate 4-alkyl/aryl-2-aminothiazoles. Mechanistic experiments demonstrated that the photocatalyst formed in situ from Cu(OAc)2 and ammonium thiocyanate promoted the intermolecular cyclization (Scheme 7). 3.2 Difunctionalization of alkenes The 1,2-difunctionalization of alkenes is a versatile

• absence of organic halide, the copper salts catalyzed the hydroamination of the alkene [59]. Mechanistic studies showed that the copper–amido complex coordinated with alkenes, which then acted as a primary photocatalyst. After light irradiation, the excited alkene–copper–amido species offered a benzyl