When metal-catalyzed C–H functionalization meets visible-light photocatalysis

• Lucas Guillemard and
• Joanna Wencel-Delord

Beilstein J. Org. Chem. 2020, 16, 1754–1804, doi:10.3762/bjoc.16.147

• similar arylation was disclosed by Balaraman et al. using eosin Y as a photoredox catalyst (Figure 24) [86]. This methodology operated under mild conditions, was efficient using a low loading of both catalysts and could be scaled-up to a gram-scale. The procedure featured a good functional tolerance and

• molecular oxygen enables to close the catalytic cycle by sequentially oxidizing the photoredox catalyst and the Pd(III) species via the formation of superoxide anion. In this way, the photocatalyst is regenerated in its ground state and the Pd(IV) intermediate undergoes fast reductive elimination

• . Furthermore, a peroxide (TBHP) is needed to oxidize the Ir-based photoredox catalyst and to generate the acyl radical via hydrogen atom transfer. From the mechanistic perspective this synergistic dual catalytic system merging C–H activation and photocatalysis is similar to the one described by Sanford for the

Heterogeneous photocatalysis in flow chemical reactors

• Christopher G. Thomson,
• Ai-Lan Lee and
• Filipe Vilela

Beilstein J. Org. Chem. 2020, 16, 1495–1549, doi:10.3762/bjoc.16.125

Photocatalyzed syntheses of phenanthrenes and their aza-analogues. A review

• Alessandra Del Tito,
• Havall Othman Abdulla,
• Davide Ravelli,
• Stefano Protti and
• Maurizio Fagnoni

Beilstein J. Org. Chem. 2020, 16, 1476–1488, doi:10.3762/bjoc.16.123

• biaryls 5.1a–d in up to excellent yields at room temperature by using α-bromoesters as radical precursors and [fac-Ir(ppy)3] as the photoredox catalyst [49]. A similar photocatalyzed tandem insertion/cyclization approach based on isocyanides and amino acid/peptide-derived Katritzky salts as precursors of

• - [55][56] phenanthridines was investigated. On the other hand, Umemoto’s reagent 7.2 was widely employed to introduce a trifluoromethyl group. In one instance, the visible-light irradiation of isocyanides 7.1 in the presence of excess 7.2 (4 equiv) and the Ru(bpy)32+ photoredox catalyst afforded the

• highly regioselective strategy for the synthesis of a library of polyheteroaromatic compounds under photocatalytic conditions was reported (Scheme 13). The process made use of fac-Ir(ppy)3 (0.3 mol %) as the photoredox catalyst and occurred at room temperature under extremely mild conditions. The

An overview on disulfide-catalyzed and -cocatalyzed photoreactions

• Yeersen Patehebieke

Beilstein J. Org. Chem. 2020, 16, 1418–1435, doi:10.3762/bjoc.16.118

• method is also applicable for the synthesis of a wide variety of cyclopentane derivatives [12]. In 2017, Huang and co-workers reported a [4 + 2] cycloaddition reaction promoted by blue LED light, using aromatic olefins as the precursor, an acridinium photoredox catalyst (Mes–Acr–Ph+BF4−), and disulfide

• photoredox catalyst or a carbocation species, which suppresses the formation of side products that are observed when using other methods. The suggested mechanism by Cheng and co-workers is shown in Scheme 16. The reaction could go through two possible pathways. The generation of the phenyl thiyl radical 43

• are used as the photoredox catalyst to prepare the corresponding primary and secondary alcohols from terminal and internal olefins. The substrate scope is broad, with excellent regioselectivities and yields up to 96% (Scheme 17). Decarboxylation reactions Carboxylic acid often serves as an inexpensive

Photocatalysis with organic dyes: facile access to reactive intermediates for synthesis

• Stephanie G. E. Amos,
• Marion Garreau,
• Luca Buzzetti and
• Jerome Waser

Beilstein J. Org. Chem. 2020, 16, 1163–1187, doi:10.3762/bjoc.16.103

• either oxidative or reductive SET with an excited photoredox catalyst. The most used scaffolds consist of electron-poor O-acyl and O-aryl hydroxylamines, which are prone to reduction, and α-N-oxy acids, which undergo oxidations followed by β-scission [128][136][139]. Leonori first described how O-aryl

Recent applications of porphyrins as photocatalysts in organic synthesis: batch and continuous flow approaches

• Rodrigo Costa e Silva,
• Luely Oliveira da Silva,
• Aloisio de Andrade Bartolomeu,
• Timothy John Brocksom and
• Kleber Thiago de Oliveira

Beilstein J. Org. Chem. 2020, 16, 917–955, doi:10.3762/bjoc.16.83

• reported a metal-free photoarylation of five-membered heteroarenes with aryldiazonium salts and meso-arylated porphyrin derivatives as photoredox catalyst [11]. Compounds such as furan, thiophene, and N-Boc-pyrrole derivatives were obtained by this methodology in 29–81% yields (Scheme 3). The key-step of

• , meta and para positions. Moreover, the methodology also showed effectiveness for heteroarenes such as pyridines and benzothiazoles. The authors also evaluated the use of NiTPP as a photoredox catalyst for other transformations involving both oxidative and reductive quenchings. The NiTPP-catalyzed

• tetrahydroquinolines by reductive quenching. Selenylation and thiolation of anilines. NiTPP as photoredox catalyst in oxidative and reductive quenching, in comparison with other photocatalysts. C–O bond cleavage of 1-phenylethanol using a cobalt porphyrin (CoTMPP) under visible light. Hydration of terminal alkynes by

Photocatalytic deaminative benzylation and alkylation of tetrahydroisoquinolines with N-alkylpyrydinium salts

• David Schönbauer,
• Carlo Sambiagio,
• Timothy Noël and
• Michael Schnürch

Beilstein J. Org. Chem. 2020, 16, 809–817, doi:10.3762/bjoc.16.74

• demonstrate the deaminative coupling of N-benzylpyridinium Katritzky salts with THIQs under ruthenium photoredox catalysis. During the preparation of this article, a similar transformation was disclosed using an iridium photoredox catalyst [47]. Results and Discussion We started our investigations by

Visible-light-induced addition of carboxymethanide to styrene from monochloroacetic acid

• Kaj M. van Vliet,
• Nicole S. van Leeuwen,
• Albert M. Brouwer and
• Bas de Bruin

Beilstein J. Org. Chem. 2020, 16, 398–408, doi:10.3762/bjoc.16.38

• solvents did not lead to any significant increase of the yield or selectivity (Table 1, entries 5–9). The reduction of catalyst loading resulted in a lower yield and a lower selectivity for the acid compound 3 (Table 1, entries 10–14). The products indicate an oxidative quenching of the photoredox catalyst

• absence of the photoredox catalyst or light, the reaction does not take place (Table 1, entries 19 and 20). Notably, during the reaction, the bright yellow color of the solution resulting from the absorption of the catalyst disappears and an insoluble precipitate is formed. The use of C6D6 as a solvent

• -yl)-10-(naphthalen-1-yl)-10H-phenoxazine instead of [Ir(ppy)3] as the photoredox catalyst had no beneficial effect on the yield or conversion, and also led to the formation of a precipitate. However, the precipitate that was formed when the organic dye 5,10-di(naphthalene-2-yl)-5,10-dihydrophenazine

Recent developments in photoredox-catalyzed remote ortho and para C–H bond functionalizations

• Rafia Siddiqui and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 248–280, doi:10.3762/bjoc.16.26

• Figure 2. The most frequently used mechanisms of converting light energy into chemical energy using photoredox catalysts are: (i) photoredox catalysis; (ii) organometallic excitation; (iii) light-induced atom transfer, and (iv) energy transfer. Basically, a photoredox catalyst transforms light energy

• dependence on external oxidants and harsh reaction conditions [83][84]. In this context, in 2014, Fabry et al. reported the use of novel dual photoredox catalytic systems made up of photoredox catalyst 11 and a rhodium catalyst to carry out the Weinreb amide C–H olefination shown in Scheme 1 [85]. By using

• this methodology, they assembled a library of compounds in good to excellent yields, with just 1 mol % of the photoredox catalyst 11 required. They observed that the yields of the products were dependent on various factors, such as the redox potential of the catalyst, the electronics of the ligand, and

Synthesis of acremines A, B and F and studies on the bisacremines

• Nils Winter and
• Dirk Trauner

Beilstein J. Org. Chem. 2019, 15, 2271–2276, doi:10.3762/bjoc.15.219

• undergo Diels–Alder reactions with electron-rich dienophiles [13][14][15][16][17], treatment of 5 with Fukuzumi’s catalyst [18] under illumination with blue light only led to decomposition of the starting material (Table 1, entry 15). Notably, a photoredox catalyst with a lower oxidation potential could

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

• Xiaowei Li,
• Xiaolin Shi,
• Xiangqian Li and
• Dayong Shi

Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218

Friedel–Crafts approach to the one-pot synthesis of methoxy-substituted thioxanthylium salts

• Kenta Tanaka,
• Yuta Tanaka,
• Mami Kishimoto,
• Yujiro Hoshino and
• Kiyoshi Honda

Beilstein J. Org. Chem. 2019, 15, 2105–2112, doi:10.3762/bjoc.15.208

• . Keywords: Friedel–Crafts reaction; metal-free conditions; one-pot synthesis; photoredox catalyst; thioxanthylium salt; Introduction Thioxanthylium salts are one of the important structural motifs found in biologically active compounds and photochemical materials [1][2][3][4][5][6][7][8]. Owing to these

Naphthalene diimides with improved solubility for visible light photoredox catalysis

• Barbara Reiß and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2019, 15, 2043–2051, doi:10.3762/bjoc.15.201

• light range between 520 nm and 640 nm. The irradiation by visible light together with the use of an organic dye instead of a transition metal complex as photoredox catalyst improve the sustainability and make photoredox catalysis “greener”. Keywords: chromophore; dyes; electrochemistry; photochemistry

• conclusively showed that there is no universal photoredox catalyst for different organic transformations. Instead, each photoredox catalyst has its own reactivity profile and scope. In order to apply organic dyes in advanced photoredox catalysts in a versatile way, it is crucial that modifications can be

• unbranched ones at the core amines gave the best combination to improve the solubility. This qualifies cNDI 6 as the best soluble potential visible light photoredox catalyst. Characterization of NDI 1, cNDI 2 and cNDI 6 The synthesized reference NDI 1 and the new cNDI 6 as potential photoredox catalyst were

Tandem copper and photoredox catalysis in photocatalytic alkene difunctionalization reactions

• Nicholas L. Reed,
• Madeline I. Herman,
• Vladimir P. Miltchev and
• Tehshik P. Yoon

Beilstein J. Org. Chem. 2019, 15, 351–356, doi:10.3762/bjoc.15.30

• describe a method for alkene oxyamination and diamination that utilizes simple carbamate and urea groups as nucleophilic heteroatom donors. This method uses a tandem copper–photoredox catalyst system that is operationally convenient. The identity of the terminal oxidant is critical in these studies. Ag(I

Oxidative radical ring-opening/cyclization of cyclopropane derivatives

• Yu Liu,
• Qiao-Lin Wang,
• Zan Chen,
• Cong-Shan Zhou,
• Bi-Quan Xiong,
• Pan-Liang Zhang,
• Chang-An Yang and
• Quan Zhou

Beilstein J. Org. Chem. 2019, 15, 256–278, doi:10.3762/bjoc.15.23

• (dtbbpy)PF4 as photocatalyst, and K2HPO4 as base in MeCN under the irradiation of 24 W blue LED light at room temperature for 12–36 h. A plausible mechanism is shown in Scheme 19. Firstly, the substrate 84a underwent oxidative quenching under the action of an iridium photoredox catalyst to afford the

N-Arylphenothiazines as strong donors for photoredox catalysis – pushing the frontiers of nucleophilic addition of alcohols to alkenes

• Fabienne Speck,
• David Rombach and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2019, 15, 52–59, doi:10.3762/bjoc.15.5

• fast access to a wide variety of catalysts. Recently it was shown that the radical cation of the photoredox catalyst can play a key role in photoinduced oxidation chemistry [16]. This is rather unusual due to the usually short lifetime of radical cations in solution attributed to their low-lying

• photoredox concept is based on the photophysical properties of the excited photoredox catalyst, the idea of the conPET concept mimics nature’s light collection system and consecutively collects the energy of two photons stored in the excited state of the initially pre-promoted photoredox catalyst’s radical

• insufficient reduction potential of the photoredox catalyst, the Markovnikov addition of alcohols through oxidative quenching is yet limited to highly activated, aromatic alkenes. To the best of our knowledge no methods are known today that allow the addition of alcohols to α-methyl-substituted styrenes

Organometallic vs organic photoredox catalysts for photocuring reactions in the visible region

• Aude-Héloise Bonardi,
• Frédéric Dumur,
• Guillaume Noirbent,
• Jacques Lalevée and
• Didier Gigmes

Beilstein J. Org. Chem. 2018, 14, 3025–3046, doi:10.3762/bjoc.14.282

• networks. Keywords: photoinitiator; photopolymerization; photoredox catalysis; photoredox catalyst; Introduction Photopolymerization reactions are now widely used both in industry and in academic laboratories. These processes usually lead to the transformation of a liquid resin in a 3D solid polymer upon

• soft irradiation [14]. 1.2 Development of photoredox catalysts In the field of photoinitiated polymerization, a photoredox catalyst is a photoinitiating system capable of regeneration during the polymerization reaction [14]. This regeneration is based on an oxidoreduction reaction between the light

• and redox reactions are possible. This process is called photoinduced electron transfer (PET). In this context, photoredox catalysis was developed. Light is used to excite the photoredox catalyst which allows electron transfer processes with additives. Both oxidation and reduction reactions can be

Cobalt- and rhodium-catalyzed carboxylation using carbon dioxide as the C1 source

• Tetsuaki Fujihara and
• Yasushi Tsuji

Beilstein J. Org. Chem. 2018, 14, 2435–2460, doi:10.3762/bjoc.14.221

• presence of [Ir(ppy)(dtbpy)](PF6) and iPr2NEt as photoredox catalyst and a sacrificial reagent, respectively, in acetonitrile under an atmospheric pressure of CO2 (Scheme 20). 1-Phenyl-1-propyne (16n) afforded hydrocarboxylated products as a mixture of regio- and stereoisomers. 4-Octyne (16b) afforded the

• reaction mechanism for these reactions. First, the Co(II) precursor is reduced to Co(I) A by the aid of an Ir photoredox catalyst and an amine under irradiation. The oxidative cyclization of A with 23 and CO2 affords cobaltacycle B (step a). Next, the protonation of B affords an intermediate C (step b

• et al. reported the Rh-catalyzed hydrocarboxylation of alkenes driven by visible-light irradiation conditions in the presence of a photoredox catalyst (Scheme 37) [75]. A model reaction using 4-cyanostyrene (40a) was carried out using iPrNEt2 as a sacrificial electron donor in the presence of [Ru(bpy

Applications of organocatalysed visible-light photoredox reactions for medicinal chemistry

• Michael K. Bogdos,
• Emmanuel Pinard and
• John A. Murphy

Beilstein J. Org. Chem. 2018, 14, 2035–2064, doi:10.3762/bjoc.14.179

• photoredox catalyst, as it will likely be able to participate in ET. 1.2.2 Brief electrochemical overview. In this review, the notation proposed by Nicewicz in his comprehensive review is adopted [35]. Therefore, all reduction potentials will be referred to using notation of the form Ex (Ox/Red) where x

Photocatalytic formation of carbon–sulfur bonds

• Alexander Wimmer and
• Burkhard König

Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4

• thiols with primary and 1,1-disubstituted alkenes. In the same year, Fadeyi et al. reported bismuth oxide (Bi2O3) as photoredox catalyst in combination with bromotrichloromethane as redox additive (Scheme 8) [38]. A series of alkyl and benzyl thiols were reacted with aliphatic alkenes and styrenes. The

• radical. Yadav and co-workers presented a metal-free radical thiol–ene approach, using benzophenone as photoredox catalyst (Scheme 13) [43]. No sacrificial oxidant is required for this reaction as benzophenone is regenerated by hydrogen atom transfer to the anti-Markovnikov radical intermediate. Aliphatic

• and aromatic thiols react under these conditions with aliphatic alkenes and styrenes. The direct C-3 sulfenylation of indoles with aryl thiols was reported by Guo, Chen and Fan, using Rose Bengal as organic photoredox catalyst and aerobic oxygen as oxidative species (Scheme 14) [44]. They propose that

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

• Hélène Guyon,
• Hélène Chachignon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2764–2799, doi:10.3762/bjoc.13.272

• electron oxidation of CF3SO2Na was performed by visible-light activated N-methyl-9-mesitylacridinium as a photoredox catalyst. Two hydrogen atom donors, 20 mol % of methyl thiosalicylate 38 for aliphatic alkenes (or 1 equiv of thiophenol 39 for styrenyl alkenes) and 2,2,2-trifluoroethanol (TFE), worked in

• presence of an iridium photoredox catalyst as reported by Zhu, Zhang and co-workers [41]. Of the photocatalysts tested, Ir[dF(CF3)ppy]2(dtbbpy)PF6 had appropriate redox potentials and gave the best results. A wide range of terminal alkenes featuring several functional groups reacted with exclusive anti

Synthesis of 1,3-cis-disubstituted sterically encumbered imidazolidinone organocatalysts

• Jan Wallbaum and
• Daniel B. Werz

Beilstein J. Org. Chem. 2017, 13, 2577–2583, doi:10.3762/bjoc.13.254

• –Crafts alkylation [23] and in combination with photoredox catalysis (Scheme 1a) [24]. The enantioselective α-alkylation was achieved by merging the common photoredox catalyst Ru(bpy)3Cl2 with imidazolidinone catalyst 3a·TfOH, controlling the stereochemistry of the radical addition via an intermediate

Copper-catalyzed asymmetric sp³ C–H arylation of tetrahydroisoquinoline mediated by a visible light photoredox catalyst

• Pierre Querard,
• Inna Perepichka,
• Eli Zysman-Colman and
• Chao-Jun Li

Beilstein J. Org. Chem. 2016, 12, 2636–2643, doi:10.3762/bjoc.12.260

• , St Andrews, Fife, KY16 9ST, UK 10.3762/bjoc.12.260 Abstract This report describes a highly enantioselective oxidative sp3 C–H arylation of N-aryltetrahydroisoquinolines (THIQs) through a dual catalysis platform. The combination of the photoredox catalyst, [Ir(ppy)2(dtbbpy)]PF6, and chiral copper

• photoredox system might help, which indeed has improved the reaction yield and enantioselectivity. Different iridium and ruthenium photoredox catalysts were evaluated and [Ir(ppy)2(dtbbpy)]PF6 was found to be the most efficient [32]. With this iridium photoredox catalyst, TBHP, and copper(I) bromide co

• toluene and THF (Table 1, entries 7 and 8). On the other hand, highly polar solvents such as MeCN and MeOH were not beneficial for the formation of the desired product 3a (Table 1, entries 9 and 10). Control experiments performed in the absence of photoredox catalyst and/or transition metal copper(II

Enantioselective additions of copper acetylides to cyclic iminium and oxocarbenium ions

• Jixin Liu,
• Srimoyee Dasgupta and
• Mary P. Watson

Beilstein J. Org. Chem. 2015, 11, 2696–2706, doi:10.3762/bjoc.11.290

• -aryltetrahydroisoquinolines with alkynes (Scheme 11) [33]. By using an iridium-based photoredox catalyst in combination with benzoyl peroxide, iminium ion 7 is formed in situ. This strategy enables reduction of the reaction temperature, ultimately enabling higher enantioselectivities. With respect to the scope of alkynes

Eosin Y-catalyzed visible-light-mediated aerobic oxidative cyclization of N,N-dimethylanilines with maleimides

• Zhongwei Liang,
• Song Xu,
• Wenyan Tian and
• Ronghua Zhang

Beilstein J. Org. Chem. 2015, 11, 425–430, doi:10.3762/bjoc.11.48

• presented the same reaction using [Ru(bpy)3]3+ as photoredox catalyst under irradiation with visible light next year [44]. Herein, we show an environmentally friendly aerobic oxidative cyclization methodology that avoids the use of metal catalysts and makes full use of air as oxidant. Results and Discussion