- Photocatalytic Metal-Organic Frameworks for Selective 2,2,2-Trifluoroethylation of Styrenes
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Synthesis of CF3-containing compounds is of great interest because of their broad use in the pharmaceutical and agrochemical industries. Herein, selective 2,2,2-trifluoroethylation of styrenes was catalyzed by Zr(IV)-based MOFs bearing visible-
- Yu, Xiao,Cohen, Seth M.
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- Understanding Ir(III) Photocatalyst Structure-Activity Relationships: A Highly Parallelized Study of Light-Driven Metal Reduction Processes
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High-throughput synthesis and screening methods were used to measure the photochemical activity of 1440 distinct heteroleptic [Ir(C^N)2(N^N)]+ complexes for the photoreduction of Sn(II) and Zn(II) cations to their corresponding neutral metals. Kinetic data collection was carried out using home-built photoreactors and measured initial rates, obtained through an automated fitting algorithm, spanned between 0-120 μM/s for Sn(0) deposition and 0-90 μM/s for Zn(0) deposition. Photochemical reactivity was compared to photophysical properties previously measured such as deaerated excited state lifetime and emission spectral data for these same complexes; however, no clear correlations among these features were observed. A formal photochemical rate law was then developed to help elucidate the observed reactivity. Initial rates were found to be directly correlated to the product of incident photon flux with three reaction elementary efficiencies: (1) the fraction of light absorbed by the photocatalyst, (2) the fraction of excited state species that are quenched by the electron donor, and (3) the cage escape efficiency. The most active catalysts exhibit high efficiencies for all three steps, and catalyst engineering requirements to maximize these elementary efficiencies were postulated. The kinetic treatment provided the mechanistic information needed to decipher the observed structure/function trends in the high-throughput work.
- Bernhard, Stefan,Connell, Timothy U.,Diluzio, Stephen,Kowalewski, Jakub F.,Mdluli, Velabo
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p. 1431 - 1444
(2022/02/05)
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- Use of Green Solvents in Metallaphotoredox Cross-Electrophile Coupling Reactions Utilizing a Lipophilic Modified Dual Ir/Ni Catalyst System
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Facilitating photoredox coupling reactions in process-friendly green solvents was achieved by the successful application of a dual Ir/Ni catalyst system with enhanced solubility properties. These photochemical reactions (specifically Br-Br sp2-
- Delgado, Pete,Duvadie, Rohit,Elmaarouf, Imran,Geraci, Gina,Glass, Raoul J.,Majumdar, Dyuti,Mikus, Malte,Robinson, Richard I.,Tan, Kian L.
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p. 17428 - 17436
(2021/12/06)
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- Stereoselective Preparation of C-Aryl Glycosides via Visible-Light-Induced Nickel-Catalyzed Reductive Cross-Coupling of Glycosyl Chlorides and Aryl Bromides
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A nickel-catalyzed cross-coupling reaction of glycosyl chlorides with aryl bromides has been developed. The reaction proceeds smoothly under visible-light irradiation and features the use of bench-stable glycosyl chlorides, allowing the highly stereoselective synthesis of C-aryl glycosides. (Figure presented.).
- Mou, Ze-Dong,Wang, Jia-Xi,Zhang, Xia,Niu, Dawen
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p. 3025 - 3029
(2021/05/27)
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- Twofold Radical-Based Synthesis of N, C-Difunctionalized Bicyclo[1.1.1]pentanes
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Bicyclo[1.1.1]pentylamines (BCPAs) are of growing importance to the pharmaceutical industry as sp3-rich bioisosteres of anilines and N-tert-butyl groups. Here we report a facile synthesis of 1,3-disubstituted BCPAs using a twofold radical functionalization strategy. Sulfonamidyl radicals, generated through fragmentation of α-iodoaziridines, undergo initial addition to [1.1.1]propellane to afford iodo-BCPAs; the newly formed C-I bond in these products is then functionalized via a silyl-mediated Giese reaction. This chemistry also translates smoothly to 1,3-disubstituted iodo-BCPs. A wide variety of radical acceptors and iodo-BCPAs are accommodated, providing straightforward access to an array of valuable aniline-like isosteres.
- Anderson, Edward A.,Mousseau, James. J.,Nugent, Jeremy,Owen, Benjamin,Pickford, Helena D.,Smith, Russell C.
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supporting information
p. 9729 - 9736
(2021/07/19)
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- PCET-Based Ligand Limits Charge Recombination with an Ir(III) Photoredox Catalyst
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Upon photoinitiated electron transfer, charge recombination limits the quantum yield of photoredox reactions for which the rates for the forward reaction and back electron transfer are competitive. Taking inspiration from a proton-coupled electron transfe
- Sayre, Hannah,Ripberger, Hunter H.,Odella, Emmanuel,Zieleniewska, Anna,Heredia, Daniel A.,Rumbles, Garry,Scholes, Gregory D.,Moore, Thomas A.,Moore, Ana L.,Knowles, Robert R.
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supporting information
p. 13034 - 13043
(2021/09/03)
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- A Water-Soluble Iridium Photocatalyst for Chemical Modification of Dehydroalanines in Peptides and Proteins
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Dehydroalanine (Dha) residues are attractive noncanonical amino acids that occur naturally in ribosomally synthesised and post-translationally modified peptides (RiPPs). Dha residues are attractive targets for selective late-stage modification of these complex biomolecules. In this work, we show the selective photocatalytic modification of dehydroalanine residues in the antimicrobial peptide nisin and in the proteins small ubiquitin-like modifier (SUMO) and superfolder green fluorescent protein (sfGFP). For this purpose, a new water-soluble iridium(III) photoredox catalyst was used. The design and synthesis of this new photocatalyst, [Ir(dF(CF3)ppy)2(dNMe3bpy)]Cl3, is presented. In contrast to commonly used iridium photocatalysts, this complex is highly water soluble and allows peptides and proteins to be modified in water and aqueous solvents under physiologically relevant conditions, with short reaction times and with low reagent and catalyst loadings. This work suggests that photoredox catalysis using this newly designed catalyst is a promising strategy to modify dehydroalanine-containing natural products and thus could have great potential for novel bioconjugation strategies.
- van Lier, Roos C. W.,de Bruijn, A. Dowine,Roelfes, Gerard
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supporting information
p. 1430 - 1437
(2020/12/11)
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- Exploiting the Reactivity of Fluorinated 2-Arylpyridines in Pd-Catalyzed C-H Bond Arylation for the Preparation of Bright Emitting Iridium(III) Complexes
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Pd-catalyzed C-H bond arylation applied to 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine (1) and 2-(3,5-difluorophenyl)-5-(trifluoromethyl)pyridine (5) allows the access to two families of Ir(III) complexes, charge-neutral and cationic species. The reaction is regioselective since only the C3- or C4-position of the fluorinated phenyl ring of 1 or 5 is readily functionalized - namely the C-H bond flanked by the two fluorine atoms which is the most acidic - which allows the electronic control of the reactive site. A range of electron-withdrawing (CN, CO2Et, C(O)Me) substituents on the aryl group has been incorporated leading to the pro-ligands (1, Ar-2,4-dFppy; 2, Ar = p-C6H4-CN; 3, Ar = p-C6H4-CO2Et; 4, Ar = p-C6H4-C(O)Me; 5, and Ar-3,5-dFppy; 6, Ar = p-C6H4-CO2Et). The unsubstituted complexes F1/G1 and F1/G5 featuring 1 and 5, respectively, as C^N ligands are used as reference complexes. The families of five charge-neutral [Ir(C^N)2(N^O)] complexes (C^N is 2-(5-aryl-(4,6-difluorophenyl)-5-(trifluoromethyl)pyridinato (F2-F4), and 2-(4-aryl-(3,5-difluorophenyl)-5-(trifluoromethyl)pyridinato (F5-F6), N^O = 2-picolinate) and five cationic [Ir(C^N)2(N^N)]PF6 complexes (N^N = dmbpy is 4,4′-dimethyl-2,2′-bipyridine) (G2-G6) were synthesized, and their structural and photophysical properties were studied with comparison to the unsubstituted analogues used as reference complexes. The appended aryl group provides large steric bulk as the biaryl fragment is twisted as shown by the X-ray crystal structures of F2, F5, F6, G3, and G5. These latter complexes display a wide variety of different Ir···Ir intermetallic distances in crystals, from 8.150 ? up to 15.034 ?. Moreover, the impact on the emission energy is negligible, as a result of the breaking of the conjugation between the two aryl groups. Charge-neutral complexes [Ir(C^N)2(N^O)] (N^O = 2-picolinate) show bright luminescence: F2-F4 (λem = 495-499 nm) are blue-green emitters, whereas F5 and F6 (λem = 537, 544 nm), where the fluorine substituents are located at the C3- and C5-positions, emit in the green region of the visible spectrum. In all cases, a unitary photoluminescence quantum yield is found. The improvement of φ might be explained by an increase of the radiative rate constant due to a higher degree of rigidity of these congested molecules, compared to the unsubstituted complex F1. The same trends are observed for the family of complexes G. Complexes G1-G4 exhibit blue photoluminescence, and G5 and G6 lead to a red-shifted emission band, as also found for the related complexes F5 and F6 due to the similar fluorine substitution pattern. Their emission quantum yields are remarkably high for charged complexes in the CH2Cl2 solution. These results showed that Pd-catalyzed C-H bond arylation is a valuable synthetic approach for designing efficient emitters with tunable photophysical properties.
- Boyaala, Rabab,Peng, Marie,Tai, Wun-Shan,Touzani, Rachid,Roisnel, Thierry,Dorcet, Vincent,Chi, Yun,Guerchais, Véronique,Doucet, Henri,Soulé, Jean-Fran?ois
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p. 13898 - 13911
(2020/10/09)
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- Catalytic Hydroetherification of Unactivated Alkenes Enabled by Proton-Coupled Electron Transfer
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We report a catalytic, light-driven method for the intramolecular hydroetherification of unactivated alkenols to furnish cyclic ether products. These reactions occur under visible-light irradiation in the presence of an IrIII-based photoredox catalyst, a Br?nsted base catalyst, and a hydrogen-atom transfer (HAT) co-catalyst. Reactive alkoxy radicals are proposed as key intermediates, generated by direct homolytic activation of alcohol O?H bonds through a proton-coupled electron-transfer mechanism. This method exhibits a broad substrate scope and high functional-group tolerance, and it accommodates a diverse range of alkene substitution patterns. Results demonstrating the extension of this catalytic system to carboetherification reactions are also presented.
- Knowles, Robert R.,Metrano, Anthony J.,Tsuchiya, Yuto,Tsui, Elaine
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p. 11845 - 11849
(2020/05/22)
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- Dearomative Photocatalytic Construction of Bridged 1,3-Diazepanes
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The construction of diverse sp3-rich skeletal ring systems is of importance to drug discovery programmes and natural product synthesis. Herein, we report the photocatalytic construction of 2,7-diazabicyclo[3.2.1]octanes (bridged 1,3-diazepanes) via a reductive diversion of the Minisci reaction. The fused tricyclic product is proposed to form via radical addition to the C4 position of 4-substituted quinoline substrates, with subsequent Hantzsch ester-promoted reduction to a dihydropyridine intermediate which undergoes in situ two-electron ring closure to form the bridged diazepane architecture. A wide scope of N-arylimine and quinoline derivatives was demonstrated and good efficiency was observed in the construction of sterically congested all-carbon quaternary centers. Computational and experimental mechanistic studies provided insights into the reaction mechanism and observed regioselectivity/diastereoselectivity.
- Dixon, Darren J.,Duarte, Fernanda,Leitch, Jamie A.,Rogova, Tatiana
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supporting information
p. 4121 - 4130
(2020/02/05)
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- Photoredox catalysed allylic trifluoromethylation via ring opening of vinyl cyclopropanes using Langlois reagent
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Trifluoromethylation of vinylcyclopropanes (VCPs) has been developed under mild reaction conditions to synthesize allylic trifluoromethylated derivatives with high yield and E/Z selectivity using visible light photo-redox catalysis and Langlois reagent (CF3SO2Na) as a trifluoromethylation source. Further, we demonstrate a gram scale synthesis procedure for a trifluoromethylation of vinylcyclopropane.
- Chandu, Palasetty,Ghosh, Krishna Gopal,Das, Debabrata,Sureshkumar, Devarajulu
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- Photocatalytic Reductive Formation of α-Tertiary Ethers from Ketals
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A general photocatalytic reductive strategy for the construction of unsymmetrical α-tertiary dialkyl ethers is reported. By merging Lewis acid-mediated ketal activation and visible-light photocatalytic reduction, in situ-generated α-alkoxy radicals were found to engage in addition reactions with a variety of olefinic partners. Good reaction efficiency is demonstrated with a range of ketals of aromatic and aliphatic ketones. Extension to acetal substrates is also described, demonstrating the overall synthetic utility of this methodology for complex ether synthesis.
- Rossolini, Thomas,Ferko, Branislav,Dixon, Darren J.
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supporting information
p. 6668 - 6673
(2019/09/03)
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- Fundamentally Different Distance Dependences of Electron-Transfer Rates for Low and High Driving Forces
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The distance dependences of electron-transfer rates (kET) in three homologous series of donor-bridge-acceptor compounds with reaction free energies (ΔGET0) of ca. -1.2, -1.6, and -2.0 eV for thermal charge recombination after initial photoinduced charge separation were studied by transient absorption spectroscopy. In the series with low driving force, the distance dependence is normal and kET decreases upon donor-acceptor distance (rDA) elongation. In the two series with higher driving forces, kET increases with increasing distance over a certain range. This counterintuitive behavior can be explained by a weakly distance-dependent electronic donor-acceptor coupling (HDA) in combination with an increasing reorganization energy (λ). Our study shows that highly exergonic electron transfers can have distance dependences that differ drastically from those of the more commonly investigated weakly exergonic reactions.
- Neumann, Svenja,Wenger, Oliver S.
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p. 855 - 860
(2019/01/11)
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- Photochemical Nickel-Catalyzed Reductive Migratory Cross-Coupling of Alkyl Bromides with Aryl Bromides
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A novel method to access 1,1-diarylalkanes from readily available, nonactivated alkyl bromides and aryl bromides via visible-light-driven nickel and iridium dual catalysis, wherein diisopropylamine (iPr2NH) is used as the terminal stoichiometric reductant, is reported. Both primary and secondary alkyl bromides can be successfully transformed into the migratory benzylic arylation products with good selectivity. Additionally, this method showcases tolerance toward a wide array of functional groups and the presence of bases.
- Peng, Long,Li, Zheqi,Yin, Guoyin
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p. 1880 - 1883
(2018/04/16)
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- Intermolecular Anti-Markovnikov Hydroamination of Unactivated Alkenes with Sulfonamides Enabled by Proton-Coupled Electron Transfer
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Here we report a catalytic method for the intermolecular anti-Markovnikov hydroamination of unactivated alkenes using primary and secondary sulfonamides. These reactions occur at room temperature under visible light irradiation and are jointly catalyzed by an iridium(III) photocatalyst, a dialkyl phosphate base, and a thiol hydrogen atom donor. Reaction outcomes are consistent with the intermediacy of an N-centered sulfonamidyl radical generated via proton-coupled electron transfer activation of the sulfonamide N-H bond. Studies outlining the synthetic scope (>60 examples) and mechanistic features of the reaction are presented.
- Zhu, Qilei,Graff, David E.,Knowles, Robert R.
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supporting information
p. 741 - 747
(2018/01/26)
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- Chemical modification of dehydrated amino acids in natural antimicrobial peptides by photoredox catalysis
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Dehydroalanine (Dha) and dehydrobutyrine (Dhb) are remarkably versatile non-canonical amino acids often found in antimicrobial peptides. This work presents the selective modification of Dha and Dhb in antimicrobial peptides through photocatalytic activation of organoborates under the influence of visible light. Ir(dF(CF3)ppy)2(dtbbpy)PF6 was used as a photoredox catalyst in aqueous solutions for the modification of thiostrepton and nisin. The mild conditions and high selectivity for the dehydrated residues show that photoredox catalysis is a promising tool for the modification of peptide-derived natural products.
- Bruijn, A. Dowine De,Roelfes, Gerard
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supporting information
p. 11314 - 11318
(2018/10/21)
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- Photocatalytic Three-Component Umpolung Synthesis of 1,3-Diamines
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A visible-light-mediated photocatalytic umpolung synthesis of 1,3-diamines from in situ-generated imines and dehydroalanine derivatives is described. Pivoting on a key nucleophilic addition of photocatalytically generated α-amino radicals to electron-deficient alkenes, this three-component coupling reaction affords 1,3-diamines efficiently and diastereoselectively. The mild protocol tolerates a wide variety of functionalities including heterocycles, pinacol boronates, and aliphatic chains. Application to biologically relevant α-amino-γ-lactam synthesis and extension to 1,3-aminoalcohols is also demonstrated.
- Rossolini, Thomas,Leitch, Jamie A.,Grainger, Rachel,Dixon, Darren J.
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p. 6794 - 6798
(2018/10/24)
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- Merging Photoredox and Organometallic Catalysts in a Metal–Organic Framework Significantly Boosts Photocatalytic Activities
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Metal–organic frameworks (MOFs) have been extensively used for single-site catalysis and light harvesting, but their application in multicomponent photocatalysis is unexplored. We report here the successful incorporation of an IrIII photoredox catalyst and a NiII cross-coupling catalyst into a stable Zr12 MOF, Zr12-Ir-Ni, to efficiently catalyze C?S bond formation between various aryl iodides and thiols. The proximity of the IrIII and NiII catalytic components to each other (ca. 0.6 nm) in Zr12-Ir-Ni greatly facilitates electron and thiol radical transfers from Ir to Ni centers to reach a turnover number of 38 500, an order of magnitude higher than that of its homogeneous counterpart. This work highlights the opportunity in merging photoredox and organometallic catalysts in MOFs to effect challenging organic transformations.
- Zhu, Yuan-Yuan,Lan, Guangxu,Fan, Yingjie,Veroneau, Samuel S.,Song, Yang,Micheroni, Daniel,Lin, Wenbin
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supporting information
p. 14090 - 14094
(2018/10/15)
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- Enantioselective Excited-State Photoreactions Controlled by a Chiral Hydrogen-Bonding Iridium Sensitizer
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Stereochemical control of electronically excited states is a long-standing challenge in photochemical synthesis, and few catalytic systems that produce high enantioselectivities in triplet-state photoreactions are known. We report herein an exceptionally effective chiral photocatalyst that recruits prochiral quinolones using a series of hydrogen-bonding and π-π interactions. The organization of these substrates within the chiral environment of the transition-metal photosensitizer leads to efficient Dexter energy transfer and effective stereoinduction. The relative insensitivity of these organometallic chromophores toward ligand modification enables the optimization of this catalyst structure for high enantiomeric excess at catalyst loadings as much as 100-fold lower than the optimal conditions reported for analogous chiral organic photosensitizers.
- Skubi, Kazimer L.,Kidd, Jesse B.,Jung, Hoimin,Guzei, Ilia A.,Baik, Mu-Hyun,Yoon, Tehshik P.
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supporting information
p. 17186 - 17192
(2017/12/06)
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- Catalytic Carbocation Generation Enabled by the Mesolytic Cleavage of Alkoxyamine Radical Cations
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A new catalytic method is described to access carbocation intermediates via the mesolytic cleavage of alkoxyamine radical cations. In this process, electron transfer between an excited state oxidant and a TEMPO-derived alkoxyamine substrate gives rise to a radical cation with a remarkably weak C?O bond. Spontaneous scission results in the formation of the stable nitroxyl radical TEMPO.as well as a reactive carbocation intermediate that can be intercepted by a wide range of nucleophiles. Notably, this process occurs under neutral conditions and at comparatively mild potentials, enabling catalytic cation generation in the presence of both acid sensitive and easily oxidized nucleophilic partners.
- Zhu, Qilei,Gentry, Emily C.,Knowles, Robert R.
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supporting information
p. 9969 - 9973
(2016/08/16)
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- Synthesis of Supramolecular Iridium Catalysts and Their Use in Enantioselective Visible-Light-Induced Reactions
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Iridium complexes were prepared which are covalently linked via a bipyridine ligand to a chiral octahydro-1H-4,7-methanoisoindol-1-one skeleton. The skeleton allows for two-point hydrogen bonding to prochiral lactams, which can be processed in iridium-catalyzed photochemical reactions. Attempts to use the iridium complexes in reactions, which typically involve photoinduced electron transfer, failed to provide the desired enantioselectivity. If employed as triplet sensitizers the complexes showed an improved performance and moderate enantioselectivities (up to 29% ee) were achieved in a photochemical epoxide rearrangement.
- B?hm, Alexander,Bach, Thorsten
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supporting information
p. 1056 - 1060
(2016/05/19)
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- Single-electron transmetalation: An enabling technology for secondary alkylboron cross-coupling
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Single-electron-mediated alkyl transfer affords a novel mechanism for transmetalation, enabling cross-coupling under mild conditions. Here, general conditions are reported for cross-coupling of secondary alkyltrifluoroborates with an array of aryl bromides mediated by an Ir photoredox catalyst and a Ni cross-coupling catalyst.
- Primer, David N.,Karakaya, Idris,Tellis, John C.,Molander, Gary A.
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supporting information
p. 2195 - 2198
(2015/03/04)
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- Facile synthesis and complete characterization of homoleptic and heteroleptic cyclometalated Iridium(III) complexes for photocatalysis
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Herein we describe an improved synthesis for homoleptic iridium(III) 2-phenylpyridine based photocatalysts that allows rapid access to these compounds in good to high yields which have recently become a vital component within the field of catalysis. In addition, we synthesized a number of heteroleptic iridium(III) 2-phenylpyridine photocatalysts and report their photophysical and electrochemical properties. The emission energies span the range of 473-560 nm and reduction potentials from -2.27 V to -1.23 V and oxidation potentials ranging from 1.81 V to 0.69 V. Additionally, we provide the calculated excited state properties and comment on the role of these properties in designing catalytic cycles.
- Singh, Anuradha,Teegardin, Kip,Kelly, Megan,Prasad, Kariate S.,Krishnan, Sadagopan,Weaver, Jimmie D.
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- Cyclometalated iridium(III) complexes as photosensitizers for long-range electron transfer: Occurrence of a coulomb barrier
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Six cyclometalated iridium(III) complexes were investigated to assess their potential as photosensitizers for long-range electron transfer, and two of them were incorporated directly into covalent donor-bridge-acceptor molecules. The influence of ligarid substitutions on the excited-state properties and the photoredox behavior of the iridium complexes was explored by optical absorption, steady-state and time-resolved luminescence spectroscopy, as well as by electrochemical methods. Bimolecular electron transfer between the photoexcited complexes and 10-methylphenothiazine and methylviologen was found to be only weakly dependent on the ligand substitutions. Intramolecular long-range electron transfer from phenothiazine to photoexcited iridium(III) in the dyads is slow due to the occurrence of a Coulomb barrier. Consequently, an electron-transfer photoproduct is only observable in the transient absorption spectrum, of a donorbridge-acceptor molecule with a fluorinated photosensitizer that exhibits a very long excited-state lifetime. A flashquench technique is necessary for detection of an electrontransfer product in the dyad with a non-fluorinated photosensitizer. The occurrence of a Coulomb barrier associated with intramolecular (excited-state) long-range electron transfer in the dyads with cyclometalated iridium(III) photosensitizers represents an important difference to previously investigated similar donor-bridge-acceptor molecules with photosensitizers based on d6 metal diimine complexes.
- Hanss, David,Freys, Jonathan C.,Bernardinelli, Gerald,Wenger, Oliver S.
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p. 4850 - 4859
(2010/05/11)
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- Synthesis, separation, and circularly polarized luminescence studies of enantiomers of iridium(III) luminophores
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A family of heteroleptic (C∧N)2Ir(acac) and homoleptic fac-Ir(C∧N)3 complexes have been synthesized and their photophysical properties studied (where C∧N = a substituted 2-phenylpyridine and acac = acetylacetonate). The neutral Δ and ∧ complexes were separated with greater than 95% enantiomeric purity by chiral supercritical fluid chromatography, and the solution circular dichroism and circularly polarized luminescence spectra for each of the enantio-enriched iridium complexes were obtained. The experimentally measured emission dissymmetries (gem) for this series compared well with predicted values provided by time-dependent density functional theory calculations. The discovered trend further showed a correlation with the dissymmetries of ionic, enantiopure hemicage compounds of Ru(II) and Zn(II), thus demonstrating the applicability of the model for predicting emission dissymmetry values across a wide range of complexes.
- Coughlin, Frederick J.,Westrol, Michael S.,Oyler, Karl D.,Byrne, Neal,Kraml, Christina,Zysman-Colman, Eli,Lowry, Michael S.,Bernhard, Stefan
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p. 2039 - 2048
(2009/01/31)
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