An integrated photocatalytic/enzymatic system for the reduction of CO₂ to methanol in bioglycerol–water

• Michele Aresta,
• Angela Dibenedetto,
• Tomasz Baran,
• Antonella Angelini,
• Przemysław Łabuz and
• Wojciech Macyk

Beilstein J. Org. Chem. 2014, 10, 2556–2565, doi:10.3762/bjoc.10.267

• , and the in situ photocatalytic reduction of NAD+ to NADH under visible-light irradiation, using semiconductors in water/bioglycerol mixtures. Bioglycerol is being produced in increasing volumes for bio-diesel production from oleaginous seeds. New applications for this product are being investigated [7

• active isomers upon visible-light irradiation in order to make the enzymatic reduction of CO2 to CH3OH viable. Results and Discussion In previous work [7] we demonstrated that encapsulated FateDH, FaldDH, and ADH enzymes are able to rapidly (<1 min) reduce CO2 in proton–donor solvents under pH-controlled

• . Therefore, we have synthesized a number of semiconducting materials showing photocatalytic activity under visible-light irradiation. The most active material was selected and fully characterized regarding its photoelectrical- and chemical-properties. Optimal conditions for use with visible light for the

Visible light photoredox-catalyzed deoxygenation of alcohols

• Daniel Rackl,
• Viktor Kais,
• Peter Kreitmeier and
• Oliver Reiser

Beilstein J. Org. Chem. 2014, 10, 2157–2165, doi:10.3762/bjoc.10.223

• lead of photochemical deoxygenations under UV light irradiation (vide supra) we envisioned carboxylic ester derivatives as substrates for initial test reactions. Benzoate esters were chosen due to the potentially very facile recovery of the benzoic acids used for activation. Through variation of the

Multichromophoric sugar for fluorescence photoswitching

• Stéphane Maisonneuve,
• Rémi Métivier,
• Pei Yu,
• Keitaro Nakatani and
• Juan Xie

Beilstein J. Org. Chem. 2014, 10, 1471–1481, doi:10.3762/bjoc.10.151

• absorption data allowed us to extrapolate the absorption spectrum of the dyad molecule in its pure closed form 2-CF, as plotted in Figure 3e (dotted line). It appears that the PSS obtained for the compound 2 with a light-irradiation at 335 nm corresponds to a mixture of 53% of 2-CF and 47% of 2-OF. Such a

Direct C–H trifluoromethylation of di- and trisubstituted alkenes by photoredox catalysis

• Ren Tomita,
• Yusuke Yasu,
• Takashi Koike and
• Munetaka Akita

Beilstein J. Org. Chem. 2014, 10, 1099–1106, doi:10.3762/bjoc.10.108

• –CF3 bonds is highly demanded. Results: The photoredox reaction of alkenes with 5-(trifluoromethyl)dibenzo[b,d]thiophenium tetrafluoroborate, Umemoto’s reagent, as a CF3 source in the presence of [Ru(bpy)3]2+ catalyst (bpy = 2,2’-bipyridine) under visible light irradiation without any additive afforded

• examination of photocatalytic trifluoromethylation of 1,1-diphenylethene 2a with 1 equivalent of Umemoto’s reagent 1a in the presence of 5 mol % fac-Ir(ppy)3, a photoredox catalyst, and 2 equivalents of K2HPO4, a base, in [D6]-DMSO under visible light irradiation (blue LEDs: λmax = 425 nm) for 2 h. As a

On the mechanism of photocatalytic reactions with eosin Y

• Michal Majek,
• Fabiana Filace and
• Axel Jacobi von Wangelin

Beilstein J. Org. Chem. 2014, 10, 981–989, doi:10.3762/bjoc.10.97

• push the acid–base equilibria of the catalytic amounts of eosin Y in either direction. The spirocyclic form EY1 contains an interrupted conjugation of the fluorone ring system and thus would be photocatalytically inactive under visible light irradiation. The neutral form EY2 exhibits only weak

Metal and metal-free photocatalysts: mechanistic approach and application as photoinitiators of photopolymerization

• Jacques Lalevée,
• Sofia Telitel,
• Pu Xiao,
• Marc Lepeltier,
• Frédéric Dumur,
• Fabrice Morlet-Savary,
• Didier Gigmes and
• Jean-Pierre Fouassier

Beilstein J. Org. Chem. 2014, 10, 863–876, doi:10.3762/bjoc.10.83

• well as the typical oxidation and reduction agents used in both reductive or oxidative cycles are gathered. The chemical mechanisms associated with various systems are also given. As compared to classical iridium-based photocatalysts which are mainly active upon blue light irradiation, a new

Visible-light photoredox catalysis enabled bromination of phenols and alkenes

• Yating Zhao,
• Zhe Li,
• Chao Yang,
• Run Lin and
• Wujiong Xia

Beilstein J. Org. Chem. 2014, 10, 622–627, doi:10.3762/bjoc.10.53

• liquid bromine. Results and Discussion Our initial investigation was carried out on protected 4-methoxyphenol 1a and CBr4 in dried CH3CN in the presence of Ru(bpy)3Cl2 (5.0 mol %) with visible light irradiation (blue LEDs, λmax = 435 nm) for 6 hours. The corresponding 2-bromo-4-methoxyphenol (2a) was

• photocatalyst or the light source did not afford the desired product 2a. Therefore, the reaction conditions of CBr4 (1 equiv) in dried CH3CN in the presence of Ru(bpy)3Cl2 (5.0 mol %) with visible light irradiation (blue LEDs, λmax = 435 nm) and open to air were utilized to test the scope of the reaction. With

• could be prepared from the same starting materials in two steps (Table 2). We also conducted a control experiment by reacting stilbene with CBr4 (1 equiv) in dry CH3CN in the presence of Ru(bpy)3Cl2 (5.0 mol %) with visible-light irradiation (blue LEDs, λmax = 435 nm) for 72 hours, which led to the anti

Continuous flow photocyclization of stilbenes – scalable synthesis of functionalized phenanthrenes and helicenes

• Quentin Lefebvre,
• Marc Jentsch and
• Magnus Rueping

Beilstein J. Org. Chem. 2013, 9, 1883–1890, doi:10.3762/bjoc.9.221

• of scalable and flexible syntheses [1][2][3][4][5]. Following the pioneering examples of Scholz [6] and Martin [7] in 1967, the photocyclization of stilbene derivatives under UV-light irradiation is now a classical method for the synthesis of phenanthrenes and helicene-like molecules [8]. However

Zinc–gold cooperative catalysis for the direct alkynylation of benzofurans

• Yifan Li and
• Jérôme Waser

Beilstein J. Org. Chem. 2013, 9, 1763–1767, doi:10.3762/bjoc.9.204

• organic materials (Figure 1). For example, members of the furocoumarin class of natural products including psoralen (1), 8-methoxypsoralen (2) and angelicin (3) can cross-link with DNA upon light irradiation. They have consequently been used for the treatment of skin diseases such as cancer or psoriasis

Organotellurium-mediated living radical polymerization under photoirradiation by a low-intensity light-emitting diode

• Yasuyuki Nakamura and
• Shigeru Yamago

Beilstein J. Org. Chem. 2013, 9, 1607–1612, doi:10.3762/bjoc.9.183

• control reached a plateau when a 10% transmittance ND filter was used, while the polymerization rate was further decelerated (Table 1, run 5). In the absence of light irradiation, the polymerization was extremely slow, reaching only 36% monomer conversion, even after 12 h (Table 1, run 6). These results

• is the origin of this rate enhancement [39]. However, the mechanism by which this occurs has not been fully elucidated. As we have deduced that the activation of ditelluride successfully proceeds under very weak intensity light irradiation, the tellanyl radical should also be formed by the photons

Metal-free aerobic oxidations mediated by N-hydroxyphthalimide. A concise review

• Lucio Melone and
• Carlo Punta

Beilstein J. Org. Chem. 2013, 9, 1296–1310, doi:10.3762/bjoc.9.146

• the photocatalytic oxidative activation of NHPI by graphitic carbon nitride (g-C3N4) and visible light irradiation [65]. g-C3N4, the most stable allotrope of carbon nitride, is a two-dimensional polymer with a tri-s-triazine ring unit and a π-conjugated layered structure similar to graphene. It is a

Photoinduced synthesis of unsymmetrical diaryl selenides from triarylbismuthines and diaryl diselenides

• Yohsuke Kobiki,
• Shin-ichi Kawaguchi,
• Takashi Ohe and
• Akiya Ogawa

Beilstein J. Org. Chem. 2013, 9, 1141–1147, doi:10.3762/bjoc.9.127

• from triarylbismuthine by near-UV light irradiation [33][54][55]. The generated aryl radical is captured by diaryl diselenide to produce diaryl selenide and a seleno radical. The seleno radical may dimerize to re-form diselenide. Diphenyl diselenide has its absorption maximum (λmax) at 340 nm (ε = 103

Spin state switching in iron coordination compounds

• Philipp Gütlich,
• Ana B. Gaspar and
• Yann Garcia

Beilstein J. Org. Chem. 2013, 9, 342–391, doi:10.3762/bjoc.9.39

• chemical nature that is important for the occurrence of spin crossover will be made. A subsequent section describes the molecular consequences of spin crossover and the variety of physical techniques usually applied for their characterization. The effects of light irradiation (LIESST) and application of

Flow photochemistry: Old light through new windows

• Jonathan P. Knowles,
• Luke D. Elliott and
• Kevin I. Booker-Milburn

Beilstein J. Org. Chem. 2012, 8, 2025–2052, doi:10.3762/bjoc.8.229

• chlorination of cyclohexane (72) with sulfuryl chloride under 15 W black-light irradiation (Scheme 23); however, the reaction was relatively inefficient and productivity was low (0.18 mmol/h) [75]. A biphasic photocyanation of pyrene (74, Scheme 24) was shown to be efficient in a polymer microchannel reactor

Control over molecular motion using the cis–trans photoisomerization of the azo group

• Estíbaliz Merino and
• María Ribagorda

Beilstein J. Org. Chem. 2012, 8, 1071–1090, doi:10.3762/bjoc.8.119

• unit of 1,1',3,3'-tetrasubstituted ferrocene, two phenyl groups as scissor blades and two phenylethylene groups as handles linked through an azobenzene [117][118]. The light irradiation of λ = 350 nm (180 min) leads to a mixture of isomers trans/cis 11:89, while exposure to visible light (λ > 400 nm

• properties are very interesting. An external stimulus, normally light irradiation at a certain wavelength, causes a fluctuation between the cis–trans isomeric species. This isomerization is reversible, photochemically and thermally. The molecular motion that occurs in the isomerization process has

Recent advances towards azobenzene-based light-driven real-time information-transmitting materials

• Jaume García-Amorós and
• Dolores Velasco

Beilstein J. Org. Chem. 2012, 8, 1003–1017, doi:10.3762/bjoc.8.113

• of an ethanol solution of azo-dye 26 generated by UV-light irradiation (λ = 355 nm, 5 ns pulse width) at 298 K ([26] = 20 μM, λobs = 420 nm). From [63] – Reproduced by permission of the Royal Society of Chemistry.

Light-induced olefin metathesis

• Yuval Vidavsky and
• N. Gabriel Lemcoff

Beilstein J. Org. Chem. 2010, 6, 1106–1119, doi:10.3762/bjoc.6.127

• products obtained by neon light irradiation of dimer 13 are highlighted in Figure 6. Perhaps the main benefit of this procedure lies in its simplicity since it only requires commercially available metal complexes and commonly used lighting equipment. An additional expansion to photopromoted RCM was

• , complexes 33a, e, f, g were irradiated at 365 nm in the presence of RCM and ROMP substrates [78]. A summary of the results is presented in Table 4 and Table 5. The discovery that light irradiation induces photoisomerisation of the cis-dichloro complexes led to the proposed mechanism shown in Scheme 7. Thus

Hybrid biofunctional nanostructures as stimuli-responsive catalytic systems

• Gernot U. Marten,
• Thorsten Gelbrich and
• Annette M. Schmidt

Beilstein J. Org. Chem. 2010, 6, 922–931, doi:10.3762/bjoc.6.98

• [4]. Other systems use a photodynamic process to force a medical effect by the photochemical drug release during light irradiation [5]. By combining thermoresponsive polymers with magnetic nanoparticles, hybrid materials become accessible that can be manipulated by two different stimuli, temperature

Novel multi-responsive P2VP-block-PNIPAAm block copolymers via nitroxide-mediated radical polymerization

• Cathrin Corten,
• Katja Kretschmer and
• Dirk Kuckling

Beilstein J. Org. Chem. 2010, 6, 756–765, doi:10.3762/bjoc.6.89

• P2VP-macroinitiator by laser light irradiation. Synthesis of the bi-responsive block copolymers. End group determination of the macroinitiators via MALDI-TOF MS. Characterization of soluble linear P2VP-block-PNIPAAm copolymers created by NMRP. Dynamic light scattering characterization of bi-responsive

Synthesis of rigidified flavin–guanidinium ion conjugates and investigation of their photocatalytic properties

• Harald Schmaderer,
• Mouchumi Bhuyan and
• Burkhard König

Beilstein J. Org. Chem. 2009, 5, No. 26, doi:10.3762/bjoc.5.26

• riboflavin 3 or compound 8. Dibenzyl phosphate esters are oxidatively cleaved by blue light irradiation (440 nm) in the presence of compounds 1 and 2 (Scheme 3). The acceleration of the reaction in acetonitrile by 1 and 2, bearing a guanidinium ion binding site with phosphate affinity, is significantly

• the presence of sacrificial electron donor substrates, such as aliphatic amines, flavins can photoreduce nitro arenes to anilines under blue light irradiation (Scheme 4). 4-Nitrophenyl phosphate was used as a substrate for photoreduction in water and in acetonitrile. The results summarized in Table 2