Showing papers on "Homolysis published in 2020"
TL;DR: It is demonstrated that α-aminoalkyl radicals, easily accessible from simple amines, promote the homolytic activation of carbon-halogen bonds with a reactivity profile mirroring that of classical tin radicals, which conveniently engages alkyl and aryl halides in a wide range of redox transformations.
Abstract: Organic halides are important building blocks in synthesis, but their use in (photo)redox chemistry is limited by their low reduction potentials. Halogen-atom transfer remains the most reliable approach to exploit these substrates in radical processes despite its requirement for hazardous reagents and initiators such as tributyltin hydride. In this study, we demonstrate that α-aminoalkyl radicals, easily accessible from simple amines, promote the homolytic activation of carbon-halogen bonds with a reactivity profile mirroring that of classical tin radicals. This strategy conveniently engages alkyl and aryl halides in a wide range of redox transformations to construct sp3-sp3, sp3-sp2, and sp2-sp2 carbon-carbon bonds under mild conditions with high chemoselectivity.
207 citations
TL;DR: In this paper, a metal-to-ligand charge transfer (MLCT) state with an energy of 1.6 eV (38 kcal/mol) was found for Ni(t-Bubpy)(o-Tol)Cl, which is representative of proposed intermediates in many Ni-photoredox reactions.
Abstract: Synthetic organic chemistry has seen major advances due to the merger of nickel and photoredox catalysis. A growing number of Ni-photoredox reactions are proposed to involve generation of excited nickel species, sometimes even in the absence of a photoredox catalyst. To gain insights about these excited states, two of our groups previously studied the photophysics of Ni(t-Bubpy)(o-Tol)Cl, which is representative of proposed intermediates in many Ni-photoredox reactions. This complex was found to have a long-lived excited state (τ = 4 ns), which was computationally assigned as a metal-to-ligand charge transfer (MLCT) state with an energy of 1.6 eV (38 kcal/mol). This work evaluates the computational assignment experimentally using a series of related complexes. Ultrafast UV-Vis and mid-IR transient absorption data suggest that a MLCT state is generated initially upon excitation but decays to a long-lived state that is 3d-d rather than 3MLCT in character. Dynamic cis,trans-isomerization of the square planar complexes was observed in the dark using 1H NMR techniques, supporting that this 3d-d state is tetrahedral and accessible at ambient temperature. Through a combination of transient absorption and NMR studies, the 3d-d state was determined to lie ∼0.5 eV (12 kcal/mol) above the ground state. Because the 3d-d state features a weak Ni-aryl bond, the excited Ni(II) complexes can undergo Ni homolysis to generate aryl radicals and Ni(I), both of which are supported experimentally. Thus, photoinduced Ni-aryl homolysis offers a novel mechanism of initiating catalysis by Ni(I).
126 citations
TL;DR: A machine learning model capable of accurately predicting BDEs for organic molecules in a fraction of a second is developed and rapidly and accurately predict major sites of hydrogen abstraction in the metabolism of drug-like molecules.
Abstract: Bond dissociation enthalpies (BDEs) of organic molecules play a fundamental role in determining chemical reactivity and selectivity. However, BDE computations at sufficiently high levels of quantum mechanical theory require substantial computing resources. In this paper, we develop a machine learning model capable of accurately predicting BDEs for organic molecules in a fraction of a second. We perform automated density functional theory (DFT) calculations at the M06-2X/def2-TZVP level of theory for 42,577 small organic molecules, resulting in 290,664 BDEs. A graph neural network trained on a subset of these results achieves a mean absolute error of 0.58 kcal mol−1 (vs DFT) for BDEs of unseen molecules. We further demonstrate the model on two applications: first, we rapidly and accurately predict major sites of hydrogen abstraction in the metabolism of drug-like molecules, and second, we determine the dominant molecular fragmentation pathways during soot formation. Bond dissociation enthalpies are key quantities in determining chemical reactivity, their computations with quantum mechanical methods being highly demanding. Here the authors develop a machine learning approach to calculate accurate dissociation enthalpies for organic molecules with sub-second computational cost.
124 citations
TL;DR: The LMCT excitation event has been investigated through a series of spectroscopic experiments, revealing a rapid bond homolysis process and an effective produc-tion of alkoxy radicals, collectively ruling out the LMCT/homolysis event as the rate determining step of this C-H functionalization.
Abstract: Modern photoredox catalysis has traditionally relied upon metal-to-ligand charge-transfer (MLCT) excitation of metal polypyridyl complexes for the utilization of light energy for the activation of organic substrates. Here, we demonstrate the catalytic application of ligand-to-metal charge-transfer (LMCT) excitation of cerium alkoxide complexes for the facile activation of alkanes utilizing abundant and inexpensive cerium trichloride as the catalyst. As demonstrated by cerium-catalyzed C-H amination and the alkylation of hydrocarbons, this reaction manifold has enabled the facile use of abundant alcohols as practical and selective hydrogen atom transfer (HAT) agents via the direct access of energetically challenging alkoxy radicals. Furthermore, the LMCT excitation event has been investigated through a series of spectroscopic experiments, revealing a rapid bond homolysis process and an effective production of alkoxy radicals, collectively ruling out the LMCT/homolysis event as the rate-determining step of this C-H functionalization.
107 citations
TL;DR: This review summarizes recent advances in the catalytic generation of alkoxy radicals from unfunctionalized alcohols and highlights current methods for O–H bond activation.
Abstract: Alkoxy radicals have long been recognized as powerful synthetic intermediates with well-established reactivity patterns. Due to the high bond dissociation free energy of aliphatic alcohol O–H bonds, these radicals are difficult to access through direct homolysis, and conventional methods have instead relied on activation of O-functionalized precursors. Over the past decade, however, numerous catalytic methods for the direct generation of alkoxy radicals from simple alcohol starting materials have emerged and created opportunities for the development of new transformations. This minireview discusses recent advances in catalytic alkoxy radical generation, with particular emphasis on progress toward the direct activation of unfunctionalized alcohols enabled by transition metal and photoredox catalysis.
86 citations
TL;DR: A direct dehydroxylative radical alkylation reaction of tertiary alcohols is reported, showing the feasibility of generating tertiary carbon radicals from alcohols and offering an approach for the facile and precise construction of all-carbon quaternary centers.
Abstract: Deoxygenative radical C-C bond-forming reactions of alcohols are a long-standing challenge in synthetic chemistry, and the current methods rely on multistep procedures. Herein, we report a direct dehydroxylative radical alkylation reaction of tertiary alcohols. This new protocol shows the feasibility of generating tertiary carbon radicals from alcohols and offers an approach for the facile and precise construction of all-carbon quaternary centers. The reaction proceeds with a broad substrate scope of alcohols and activated alkenes. It can tolerate a wide range of electrophilic coupling partners, including allylic carboxylates, aryl and vinyl electrophiles, and primary alkyl chlorides/bromides, making the method complementary to the cross-coupling procedures. The method is highly selective for the alkylation of tertiary alcohols, leaving secondary/primary alcohols (benzyl alcohols included) and phenols intact. The synthetic utility of the method is highlighted by its 10-g-scale reaction and the late-stage modification of complex molecules. A combination of experiments and density functional theory calculations establishes a plausible mechanism implicating a tertiary carbon radical generated via Ti-catalyzed homolysis of the C-OH bond.
67 citations
TL;DR: The H2O2 reaction with reduced Hypocrea jecorina LPMO 9A (CuI-HjLPMO9A) is demonstrated to be 1,000-fold faster than the O2 reaction while producing the same oxidized oligosaccharide products.
Abstract: Lytic polysaccharide monooxygenases (LPMOs) have been proposed to react with both O 2 and H 2 O 2 as cosubstrates. In this study, the H 2 O 2 reaction with reduced Hypocrea jecorina LPMO9A (CuI-HjLPMO9A) is demonstrated to be 1,000-fold faster than the O 2 reaction while producing the same oxidized oligosaccharide products. Analysis of the reactivity in the absence of polysaccharide substrate by stopped-flow absorption and rapid freeze–quench (RFQ) electron paramagnetic resonance (EPR) and magnetic circular dichroism (MCD) yields two intermediates corresponding to neutral tyrosyl and tryptophanyl radicals that are formed along minor reaction pathways. The dominant reaction pathway is characterized by RFQ EPR and kinetic modeling to directly produce CuII-HjLPMO9A and indicates homolytic O–O cleavage. Both optical intermediates exhibit magnetic exchange coupling with the CuII sites reflecting facile electron transfer (ET) pathways, which may be protective against uncoupled turnover or provide an ET pathway to the active site with substrate bound. The reactivities of nonnative organic peroxide cosubstrates effectively exclude the possibility of a ping-pong mechanism.
65 citations
TL;DR: An unparalleled example of switching between homolytic and heterolytic HER mechanisms is reported, designed and synthesized three nickel(II) porphyrins with distinct steric effects by introducing bulky amido moieties to ortho- or para-positions of the meso-phenyl groups.
Abstract: Several H-H bond forming pathways have been proposed for the hydrogen evolution reaction (HER). Revealing these HER mechanisms is of fundamental importance for the rational design of catalysts and is also extremely challenging. Now, an unparalleled example of switching between homolytic and heterolytic HER mechanisms is reported. Three nickel(II) porphyrins were designed and synthesized with distinct steric effects by introducing bulky amido moieties to ortho- or para-positions of the meso-phenyl groups. These porphyrins exhibited different catalytic HER behaviors. For these Ni porphyrins, although their 1e-reduced forms are active to reduce trifluoroacetic acid, the resulting Ni hydrides (depending on the steric effects of porphyrin rings) have different pathways to make H2 . Understanding HER processes, especially controllable switching between homolytic and heterolytic H-H bond formation pathways through molecular engineering, is unprecedented in electrocatalysis.
65 citations
TL;DR: This method provides access to products with readily enolizable functional groups, incompatible with traditional Pd-catalyzed conditions, and offers access to valuable oxindole and isoindoline-1-one motifs.
Abstract: A mild visible-light-induced Pd-catalyzed intramolecular C-H arylation of amides is reported. The method operates by cleavage of a C(sp2 )-O bond, leading to hybrid aryl Pd-radical intermediates. The following 1,5-hydrogen atom translocation, intramolecular cyclization, and rearomatization steps lead to valuable oxindole and isoindoline-1-one motifs. Notably, this method provides access to products with readily enolizable functional groups that are incompatible with traditional Pd-catalyzed conditions.
61 citations
TL;DR: Mechanical studies show that the ready formation of chlorine atom radicals is responsible for the facile formation of C-Cl bonds in this synthetic process, which exhibits a wide substrate scope, excellent functional group tolerance, extraordinarily mild conditions and does not require external ligands.
Abstract: This work demonstrates photoredox vicinal dichlorination of alkenes, based on the homolysis of CuCl2 in response to irradiation with visible light. This catalysis proceeds via a ligand to metal charge transfer process and provides an exciting opportunity for the synthesis of 1,2-dichloride compounds using an inexpensive, low-molecular-weight chlorine source. This new process exhibits a wide substrate scope, excellent functional group tolerance, extraordinarily mild conditions and does not require external ligands. Mechanistic studies show that the ready formation of chlorine atom radicals is responsible for the facile formation of C-Cl bonds in this synthetic process.
58 citations
TL;DR: In this article, the authors investigated the possible pathways of indole pyrolysis to form HCN and NH3 using the density functional theory (DFT) method and found that the path-1 is the optimal reaction pathway.
Abstract: Coal is a major contributor to the global emission of nitrogen oxides. The NOx formation during coal utilisation typically derives from thermal decomposition of N-containing compounds pyrrole, which usually combines with an aromatic ring in the form of indole. NH3 and HCN are common precursors of NOx from the decomposition of N-containing compounds. In this study, possible pathways of indole pyrolysis to form HCN and NH3 are investigated using the density functional theory (DFT) method. Calculation results indicate that indole pyrolysis has two type of possible initial reactions, which are internal hydrogen transfer and hydrogen homolysis reaction, respectively. The initial reaction mode of indole has a great impact on the subsequent pyrolysis pathway. Additionally, it is shown that indole can produce two nitrogen-containing products, i.e. HCN and NH3. Five pathways will result in the formation of HCN (path-1, path-3, path-a, path-b, path-c), and another two pathways will lead to the NH3 (path-2, path-4). Furthermore, among all the reaction mechanisms of indole pyrolysis, the path-1 is the optimal reaction pathway. During which, indole is converted to a diradical intermediate, then the intermediate undergoes a synergy ring-opening transition state to form a new intermediate. Afterwards, the new intermediate decomposes into CN by homolysis of the C–C bond.
TL;DR: Preliminary mechanistic and radical trapping studies with primary alkyl bromides suggest a unique mode of tertiary C-radical generation through chain-walking followed by Ni–C bond homolysis, which enables the expedient formation of quaternary centers from easily available starting materials.
Abstract: Despite remarkable recent advances in transition-metal-catalyzed C(sp3)−C cross-coupling reactions, there remain challenging bond formations. One class of such reactions include the formation of tertiary-C(sp3)−C bonds, presumably due to unfavorable steric interactions and competing isomerizations of tertiary alkyl metal intermediates. Reported herein is a Ni-catalyzed migratory 3,3-difluoroallylation of unactivated alkyl bromides at remote tertiary centers. This approach enables the facile construction of otherwise difficult to prepare all-carbon quaternary centers. Key to the success of this transformation is an unusual remote functionalization via chain walking to the most sterically hindered tertiary C(sp3) center of the substrate. Preliminary mechanistic and radical trapping studies with primary alkyl bromides suggest a unique mode of tertiary C-radical generation through chain-walking followed by Ni–C bond homolysis. This strategy is complementary to the existing coupling protocols with tert-alkyl organometallic or -alkyl halide reagents, and it enables the expedient formation of quaternary centers from easily available starting materials. Formation of tertiary C(sp3)-C bonds is a formidable challenge due to steric interactions and low barriers for isomerization of intermediates. Here, the authors show a Ni-catalyzed migratory 3,3-difluoroallylation of unactivated alkyl bromides at remote tertiary carbon centers.
TL;DR: The mechanical dissociation of an N-heterocyclic carbene precursor has been shown to proceed with the rupture of a C–C bond through concomitant heterolytic, concerted and homolytic pathways.
Abstract: Chemical reactions usually proceed through a radical, concerted or ionic mechanism; transformations in which all three mechanisms occur are rare. In polymer mechanochemistry, a mechanical force, transduced along polymer chains, is used to activate covalent bonds in mechanosensitive molecules (mechanophores). Cleavage of a C–C bond often follows a homolytic pathway, but some mechanophores have also been designed that react in a concerted or, more rarely, a heterolytic manner. Here, using 1H- and 19F-nuclear magnetic resonance spectroscopy in combination with deuterium labelling, we show that the dissociation of a mechanophore built around an N-heterocyclic carbene precursor proceeds with the rupture of a C–C bond through concomitant heterolytic, concerted and homolytic pathways. The distribution of products probably arises from a post-transition-state bifurcation in the reaction pathway, and their relative proportion is dictated by the polarization of the scissile C–C bond. Chemical reactions usually proceed through either a radical, concerted or ionic mechanism; transformations in which all three mechanisms occur are rare. Now, the mechanical dissociation of an N-heterocyclic carbene precursor has been shown to proceed with the rupture of a C–C bond through concomitant heterolytic, concerted and homolytic pathways.
TL;DR: A catalytic, light-driven protocol for the intramolecular hydroetherification of unactivated alkenols to furnish cyclic ether products that accommodates a diverse range of alkene substitution patterns.
Abstract: 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 Bronsted 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.
TL;DR: The Cα–Cβ bond in homoallylic alcohols can be activated under basic conditions, qualifying these nonstrained acyclic systems as radical allylation reagents, and the role of base in the C–C bond activation is studied by computation.
Abstract: The Cα-Cβ bond in homoallylic alcohols can be activated under basic conditions, qualifying these nonstrained acyclic systems as radical allylation reagents. This reactivity is exemplified by photoinitiated (with visible light and/or blue LEDs) allylation of perfluoroalkyl and alkyl radicals generated from perfluoroalkyl iodides and alkylpyridinium salts, respectively, with homoallylic alcohols. C-radical addition to the double bond of the title reagents and subsequent base-promoted homolytic Cα-Cβ cleavage leads to the formation of the corresponding allylated products along with ketyl radicals that act as single electron reductants to sustain the chain reactions. Substrate scope is documented and the role of base in the C-C bond activation is studied by computation.
TL;DR: The combined results from static spectroscopic investigations and conventional photochemistry, ultrafast transient absorption, and electron paramagnetic resonance (EPR) spin trapping experiments, strongly support blue light induced Cu-Cl homolytic bond cleavage occurring in [Cu(dmp)2Cl]+ occurring in less than 100 femtoseconds.
Abstract: Developments in the field of photoredox catalysis that leveraged the long-lived excited states of Ir(III) and Ru(II) photosensitizers to enable radical coupling processes paved the way for explorations of synthetic transformations that would otherwise remain unrealized. While first row transition metal photocatalysts have not been as extensively investigated, valuable synthetic transformations covering broad scopes of olefin functionalization have been recently reported featuring photoactivated chlorobis(phenanthroline) Cu(II) complexes. In this study, the photochemical processes underpinning the catalytic activity of [Cu(dmp)2Cl]Cl (dmp = 2,9-dimethyl-1,10-phenanthroline) were studied. The combined results from static spectroscopic measurements and conventional photochemistry, ultrafast transient absorption, and electron paramagnetic resonance spin trapping experiments strongly support blue light (λex = 427 or 470 nm)-induced Cu-Cl homolytic bond cleavage in [Cu(dmp)2Cl]+ occurring in <100 fs. On the basis of electronic structure calculations, this bond-breaking photochemistry corresponds to the Cl → Cu(II) ligand-to-metal charge transfer transition, unmasking a Cu(I) species [Cu(dmp)2]+ and a Cl atom, thereby serving as a departure point for both Cu(I)- or Cu(II)-based photoredox transformations. No net photochemistry was observed through direct excitation of the ligand-field transitions in the red (λex = 785 or 800 nm), and all combined experiments indicated no evidence of Cu-Cl bond cleavage under these conditions. The underlying visible light-induced homolysis of a metal-ligand bond yielding a one-electron-reduced photosensitizer and a radical species may form the basis for novel transformations initiated by photoinduced homolysis featuring in situ-formed metal-substrate adducts utilizing first row transition metal complexes.
TL;DR: Olive and camellia oils were monitored and compared during heating at 120°C, 150°C and 180°C for 24h to determine the possible thermal oxidation mechanism of oleic acid triglyceride as discussed by the authors.
Abstract: Olive and camellia oils were monitored and compared during heating at 120 °C, 150 °C and 180 °C for 24 h to determine the possible thermal oxidation mechanism of oleic acid triglyceride. The results demonstrated that octanal, nonanal, decanal, 2-decenal and 2-undecenal were the characteristic carbonyls for oleic acid-rich oils. The oxidation rule of oil was easily determined at 120 °C, at which point changes in the acid value, peroxide value, anisidine value and carbonyl compounds corresponded to changes in fatty acids and tocopherols. However, the oxidation rule of oil was different at higher temperatures. According to the evolution of five characteristic aldehydes, four types of oxidation pathways of oleic acid triglyceride were obtained: Decanal and 2-undecenal came from the homolysis of 8- hydroperoxide. Nonanal was from the homolysis of 10- hydroperoxide and 9- hydroperoxide. Octanal was from the homolysis of 11- hydroperoxide. 2-Decenal was from the homolysis of 9- hydroperoxide. Homolysis B-scission of 10-hydroperoxide (nonanal), 11-hydroperoxide (octanal) and 8- hydroperoxide (decanal) was predominant at 120 °C, but was weakened as the temperature increased to 180 °C. Hence, the temperature had a significant effect on the formation and decomposition of hydroperoxide positional isomers.
TL;DR: It is demonstrated that the intermediary instalment of a carbon-iodine bond sets the strategic basis for an Umpolung and thereby establishes an unprecedented nucleophilic fluorination pathway.
Abstract: Iodine catalysis was developed for aliphatic fluorination through light-promoted homolytic C-H bond cleavage. The intermediary formation of amidyl radicals enables selective C-H functionalization via carbon-centered radicals. For the subsequent C-F bond formation, previous methods have typically been limited by a requirement for electrophilic fluorine reagents. We here demonstrate that the intermediary instalment of a carbon-iodine bond sets the stage for an umpolung, thereby establishing an unprecedented nucleophilic fluorination pathway.
TL;DR: Methylbismuth, the first organometallic non-stabilized bismuth(i) compound, was generated in the gas phase and characterized and implications for its chemistry in the condensed phase were investigated.
Abstract: We report the generation, spectroscopic characterization, and computational analysis of the first free (non-stabilized) organometallic bismuthinidene, BiMe. The title compound was generated in situ from BiMe3 by controlled homolytic Bi–C bond cleavage in the gas phase. Its electronic structure was characterized by a combination of photoion mass-selected threshold photoelectron spectroscopy and DFT as well as multi-reference computations. A triplet ground state was identified and an ionization energy (IE) of 7.88 eV was experimentally determined. Methyl abstraction from BiMe3 to give [BiMe2]• is a key step in the generation of BiMe. We reaveal a bond dissociation energy of 210 ± 7 kJ mol−1, which is substantially higher than the previously accepted value. Nevertheless, the homolytic cleavage of Me–BiMe2 bonds could be achieved at moderate temperatures (60–120 °C) in the condensed phase, suggesting that [BiMe2]• and BiMe are accessible as reactive intermediates under these conditions.
TL;DR: Mechanistic analysis suggests that oxidative turnover of the iridium amino trihydride (PNHP)Ir(H)3 (IrH 2, PNHP = bis[2-diisopropylphosphino)ethyl]amine) to IrN 1 proceeds through two successive hydrogen atom transfers (HAT) to 2 equiv of phenoxyl that are generated transiently at the anode.
Abstract: Electron-rich phenols, including α-rac-tocopherol Ar1OH, 2,4,6,-tri-tert-butylphenol Ar3OH, and butylated hydroxy-toluene Ar4OH, are effective electrochemical mediators for the electrocatalytic oxidation of alcohols by an iridium amido dihyride complex (PNP)Ir(H)2 (IrN 1, PNP = bis[2-diisopropylphosphino)ethyl]amide). Addition of phenol mediators leads to a decrease in the onset potential of catalysis from -0.65 V vs Fc+/0 under unmediated conditions to -1.07 V vs Fc+/0 in the presence of phenols. Mechanistic analysis suggests that oxidative turnover of the iridium amino trihydride (PNHP)Ir(H)3 (IrH 2, PNHP = bis[2-diisopropylphosphino)ethyl]amine) to IrN 1 proceeds through two successive hydrogen atom transfers (HAT) to 2 equiv of phenoxyl that are generated transiently at the anode. Isotope studies and comparison to known systems are consistent with initial homolysis of an Ir-H bond being rate-determining. Turnover frequencies up to 14.6 s-1 and an average Faradaic efficiency of 93% are observed. The mediated system shows excellent chemoselectivity in bulk oxidations of 2-propanol and 1,2-benzenedimethanol in THF and is also viable in neat 2-propanol.
TL;DR: It is shown that synthetic [Fe4S4]-alkyl clusters undergo Fe-C bond homolysis when the alkylated Fe site has a suitable coordination number, providing support for the intermediacy of organometallic species in radical SAM enzymes.
Abstract: All kingdoms of life use the transient 5'-deoxyadenosyl radical (5'-dAdo•) to initiate a wide range of difficult chemical reactions. Because of its high reactivity, the 5'-dAdo• must be generated in a controlled manner to abstract a specific H atom and avoid unproductive reactions. In radical S-adenosylmethionine (SAM) enzymes, the 5'-dAdo• is formed upon reduction of SAM by an [Fe4S4] cluster. An organometallic precursor featuring an Fe-C bond between the [Fe4S4] cluster and the 5'-dAdo group was recently characterized and shown to be competent for substrate radical generation, presumably via Fe-C bond homolysis. Such reactivity is without precedent for Fe-S clusters. Here, we show that synthetic [Fe4S4]-alkyl clusters undergo Fe-C bond homolysis when the alkylated Fe site has a suitable coordination number, thereby providing support for the intermediacy of organometallic species in radical SAM enzymes. Addition of pyridine donors to [(IMes)3Fe4S4-R]+ clusters (R = alkyl or benzyl; IMes = 1,3-dimesitylimidazol-2-ylidene) generates R•, ultimately forming R-R coupled hydrocarbons. This process is facile at room temperature and allows for the generation of highly reactive radicals including primary carbon radicals. Mechanistic studies, including use of the 5-hexenyl radical clock, demonstrate that Fe-C bond homolysis occurs reversibly. Using these experimental insights and kinetic simulations, we evaluate the circumstances in which an organometallic intermediate can direct the 5'-dAdo• toward productive H-atom abstraction. Our findings demonstrate that reversible homolysis of even weak M-C bonds is a feasible protective mechanism for the 5'-dAdo• that can allow selective X-H bond activation in both radical SAM and adenosylcobalamin enzymes.
TL;DR: The unique non‐planar structure of the pyridinium intermediate, provides the necessary driving force for the aryl radical formation and permits borylation of a wide variety of aromatic amines indistinctively of the electronic environment.
Abstract: Herein, we report a radical borylation of aromatic amines through a homolytic C(sp2 )-N bond cleavage. This method capitalizes on a simple and mild activation via a pyrylium reagent (Sc Pyry-OTf) thus priming the amino group for reactivity. The combination of terpyridine and a diboron reagent triggers a radical reaction which cleaves the C(sp2 )-N bond and forges a new C(sp2 )-B bond. The unique non-planar structure of the pyridinium intermediate, provides the necessary driving force for the aryl radical formation. The method permits borylation of a wide variety of aromatic amines indistinctively of the electronic environment.
TL;DR: A decarboxylative borylation of aliphatic acids for the synthesis of a variety of alkylboronates has been developed by mixing m-chloroperoxybenzoic acid (mCPBA)-activated fatty acids with bis(catecholato)diboron in N,N-dimethylformamide (DMF) at room temperature.
TL;DR: In this paper, the authors used CTA for organotellurium-mediated radical polymerization (TERP) and showed that CTA is highly photosensitive and generates radicals by carbon-tellurium bond homolysis upon carbon- tellurium ionization.
Abstract: Organotellurium chain transfer agents (CTAs) used for organotellurium-mediated radical polymerization (TERP) are highly photosensitive and generate radicals by carbon-tellurium bond homolysis upon ...
TL;DR: The selective photocatalytic energy-transfer-driven homolysis followed by decarboxylation generates the persistent iminyl radical and aryl radical, which would undergo an unprecedented intermolecular hydrogen atom abstraction from the alkyl substrate to provide the key C(sp3) radical.
TL;DR: It was demonstrated that alkyl radicals could also be engaged into cascades consisting of an intermolecular Giese‐type addition followed by an intramolecular homolytic aromatic substitution to rapidly assemble valuable azepinoindolones.
Abstract: In this work, a photocatalytic strategy for a rapid and modular access to polycyclic indolones starting from readily available indoles is reported. This strategy relies on the use of redox-active esters in combination with an iridium-based photocatalyst under visible-light irradiation. The generation of alkyl radicals through decarboxylative single electron reductions enables intramolecular homolytic aromatic substitutions with a pending indole moiety to afford pyrrolo- and pyridoindolone derivatives under mild conditions. Furthermore, it was demonstrated that these radicals could also be engaged into cascades consisting of an intermolecular Giese-type addition followed by an intramolecular homolytic aromatic substitution to rapidly assemble valuable azepinoindolones.
TL;DR: A strategy for controlling the bond dissociation process of the excited state of photochromic systems is given, and the strategy enables to develop further novel radical and zwitterionic photoswitches.
Abstract: Photochromic materials have been widely used in various research fields because of their variety of photoswitching properties based on various molecular frameworks and bond breaking processes, such as homolysis and heterolysis. However, while a number of photochromic molecular frameworks have been reported so far, there are few reports on photochromic molecular frameworks that show both homolysis and heterolysis depending on the substituents with high durability. The biradicals and zwitterions generated by homolysis and heterolysis have different physical and chemical properties and different potential applications. Therefore, the rational photochromic molecular design to control the bond dissociation in the excited state on demand expands the versatility for photoswitch materials beyond the conventional photochromic molecular frameworks. In this study, we synthesized novel photochromic molecules based on the framework of a radical-dissociation-type photochromic molecule: phenoxyl-imidazolyl radical complex (PIC). While the conventional PIC shows the photoinduced homolysis, the substitution of a strong electron-donating moiety to the phenoxyl moiety enables the bond dissociation process to be switched from homolysis to heterolysis. This study gives a strategy for controlling the bond dissociation process of the excited state of photochromic systems, and the strategy enables us to develop further novel radical and zwitterionic photoswitches.
TL;DR: In this paper, the authors evaluated FeS as a heterogeneous activator for peroxydisulfate (PS) with trichloroethene (TCE) chosen as model substance representing organic water pollutants prone to fast oxidation by sulfate radicals.
TL;DR: It is shown that mechanical stress on collagen produces radicals and subsequently reactive oxygen species and suggested that collagen I evolved as a radical sponge against mechano-oxidative damage, and a mechanism for exercise-induced oxidative stress and redox-mediated pathophysiological processes is proposed.
Abstract: As established nearly a century ago, mechanoradicals originate from homolytic bond scission in polymers. The existence, nature and biological relevance of mechanoradicals in proteins, instead, are unknown. We here show that mechanical stress on collagen produces radicals and subsequently reactive oxygen species, essential biological signaling molecules. Electron-paramagnetic resonance (EPR) spectroscopy of stretched rat tail tendon, atomistic molecular dynamics simulations and quantum-chemical calculations show that the radicals form by bond scission in the direct vicinity of crosslinks in collagen. Radicals migrate to adjacent clusters of aromatic residues and stabilize on oxidized tyrosyl radicals, giving rise to a distinct EPR spectrum consistent with a stable dihydroxyphenylalanine (DOPA) radical. The protein mechanoradicals, as a yet undiscovered source of oxidative stress, finally convert into hydrogen peroxide. Our study suggests collagen I to have evolved as a radical sponge against mechano-oxidative damage and proposes a mechanism for exercise-induced oxidative stress and redox-mediated pathophysiological processes.
TL;DR: The homolytic activation of alcohols and amines allows atom‐efficient, additive‐free cross‐coupling and transfer hydrogenation under mild reaction conditions with usually unreactive, yet desirable reagents, including esters and bis(pinacolato)diboron.
Abstract: The homolytic cleavage of O-H and N-H or weak C-H bonds is a key elementary step in redox catalysis, but is thought to be unfeasible for palladium. In stark contrast, reported here is the room temperature and reversible oxidative addition of water, isopropanol, hexafluoroisopropanol, phenol, and aniline to a palladium(0) complex with a cyclic (alkyl)(amino)carbene (CAAC) and a labile pyridino ligand, as is also the case in popular N-heterocyclic carbene (NHC) palladium(II) precatalysts. The oxidative addition of protic solvents or adventitious water switches the chemoselectivity in catalysis with alkynes through activation of the terminal C-H bond. Most salient, the homolytic activation of alcohols and amines allows atom-efficient, additive-free cross-coupling and transfer hydrogenation under mild reaction conditions with usually unreactive, yet desirable reagents, including esters and bis(pinacolato)diboron.