Showing papers on "Homolysis published in 2022"

Metalloporphyrins as Catalytic Models for Studying Hydrogen and Oxygen Evolution and Oxygen Reduction Reactions.

Abstract: ConspectusThe hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) are involved in biological and artificial energy conversions. H-H and O-O bond formation/cleavage are essential steps in these reactions. In nature, intermediates involved in the H-H and O-O bond formation/cleavage are highly reactive and short-lived, making their identification and investigation difficult. In artificial catalysis, the realization of these reactions at considerable rates and close to their thermodynamic reaction equilibria remains a challenge. Therefore, the elucidation of the reaction mechanisms and structure-function relationships is of fundamental significance to understand these reactions and to develop catalysts.This Account describes our recent investigations on catalytic HER, OER, and ORR with metalloporphyrins and derivatives. Metalloporphyrins are used in nature for light harvesting, energy conversion, electron transfer, O2 activation, and peroxide degradation. Synthetic metal porphyrin complexes are shown to be active for these reactions. We focused on exploring metalloporphyrins to study reaction mechanisms and structure-function relationships because they have stable and tunable structures and characteristic spectroscopic properties.For HER, we identified three H-H bond formation mechanisms and established the correlation between these processes and metal hydride electronic structures. Importantly, we provided direct experimental evidence for the bimetallic homolytic H-H bond formation mechanism by using sterically bulky porphyrins. Homolytic HER has been long proposed but rarely verified because the coupling of active hydride intermediates occurs spontaneously and quickly, making their detection challenging. By blocking the bimolecular mechanism through steric effects, we stabilized and characterized the NiIII-H intermediate and verified homolytic HER by comparing the reaction behaviors of Ni porphyrins with and without steric effects. We therefore provided an unprecedented example to control homolytic versus heterolytic HER mechanisms through tuning steric effects of molecular catalysts.For the OER, the water nucleophilic attack (WNA) on high-valent terminal Mn-oxo has been proposed for the O-O bond formation in natural and artificial water oxidation. By using Mn tris(pentafluorophenyl)corrole, we identified MnV(O) and MnIV-peroxo intermediates in chemical and electrochemical OER and provided direct experimental evidence for the Mn-based WNA mechanism. Moreover, we demonstrated several catalyst design strategies to enhance the WNA rate, including the pioneering use of protective axial ligands. By studying Cu porphyrins, we proposed a bimolecular coupling mechanism between two metal-hydroxide radicals to form O-O bonds. Note that late-transition metals do not likely form terminal metal-oxo/oxyl.For the ORR, we presented several strategies to improve activity and selectivity, including providing rapid electron transfer, using electron-donating axial ligands, introducing hydrogen-bonding interactions, constructing dinuclear cooperation, and employing porphyrin-support domino catalysis. Importantly, we used Co porphyrin atropisomers to realize both two-electron and four-electron ORR, representing an unparalleled example to control ORR selectivity by tuning only steric effects without modifying molecular and/or electronic structures.Lastly, we developed several strategies to graft metalloporphyrins on various electrode materials through different covalent bonds. The molecular-engineered materials exhibit boosted electrocatalytic performance, highlighting promising applications of molecular electrocatalysis. Taken together, this Account demonstrates the benefits of exploring metalloporphyrins for the HER, OER, and ORR. The knowledge learned herein is valuable for the development of porphyrin-based catalysts and also other molecular and material catalysts for small molecule activation reactions.

Chemical Upcycling of Commercial Polystyrene via Catalyst-Controlled Photooxidation.

Abstract: Chemical upcycling of polystyrene into targeted small molecules is desirable to reduce plastic pollution. Herein, we report the upcycling of polystyrene to benzoyl products, primarily benzoic acid, using a catalyst-controlled photooxidative degradation method. FeCl3 undergoes a homolytic cleavage upon irradiation with white light to generate a chlorine radical, abstracting an electron-rich hydrogen atom on the polymer backbone. Under the oxygen-rich environment, high MW polystyrene (>90 kg/mol) degrades down to <1 kg/mol and produces up to 23 mol % benzoyl products. A series of mechanistic studies showed that chlorine radicals promoted the degradation via hydrogen-atom abstraction. Commercial polystyrene degrades efficiently in our method, showing the compatibility of our system with polymer fillers. Finally, we demonstrated the potential of scaling up our approach in a photoflow process to convert gram quantities of PS to benzoic acid.

Heterolytic Dissociation of H2 in Heterogeneous Catalysis

Abstract: H2 dissociation plays crucial roles in catalytic hydrogenation reactions and hydrogen storage. Metal-nanoparticle-based heterogeneous catalysts often dissociate H2 via a homolytic pathway. The heterolytic H2 dissociation pathway was identified in several heterogeneous catalytic systems, including single-atom catalysts, metal–support interfaces, and bulk metal oxides/sulfides/nitrides/phosphides. The active site structures of these heterogeneous catalysts resemble homogeneous catalysts where the metal centers (Lewis acids) are coordinated with O/S/N/P atoms (Lewis bases). These Lewis acid–base pairs dissociate H2 molecules heterolytically into proton–hydride pairs, which favor the hydrogenation of polar functional groups in unsaturated hydrocarbons. In this review, we summarize the common structural features of heterogeneous, homogeneous, and enzyme catalysts in the heterolytic dissociation of H2. The active sites, Lewis acid–base pairs, are discussed throughout this review. The energy barriers and kinetic contributions of heterolytic and homolytic H2 dissociation pathways in heterogeneous catalytic systems are discussed. The spectroscopic evidence of the heterolytic H2 dissociation pathways is critically reviewed.

Elucidating the Mechanism of Excited-State Bond Homolysis in Nickel-Bipyridine Photoredox Catalysts.

Abstract: Ni 2,2'-bipyridine (bpy) complexes are commonly employed photoredox catalysts of bond-forming reactions in organic chemistry. However, the mechanisms by which they operate are still under investigation. One potential mode of catalysis is via entry into Ni(I)/Ni(III) cycles, which can be made possible by light-induced, excited-state Ni(II)-C bond homolysis. Here, we report experimental and computational analyses of a library of Ni(II)-bpy aryl halide complexes, Ni(Rbpy)(R'Ph)Cl (R = MeO, t-Bu, H, MeOOC; R' = CH3, H, OMe, F, CF3), to illuminate the mechanism of excited-state bond homolysis. At given excitation wavelengths, photochemical homolysis rate constants span 2 orders of magnitude across these structures and correlate linearly with Hammett parameters of both bpy and aryl ligands, reflecting structural control over key metal-to-ligand charge-transfer (MLCT) and ligand-to-metal charge-transfer (LMCT) excited-state potential energy surfaces (PESs). Temperature- and wavelength-dependent investigations reveal moderate excited-state barriers (ΔH‡ ∼ 4 kcal mol-1) and a minimum energy excitation threshold (∼55 kcal mol-1, 525 nm), respectively. Correlations to electronic structure calculations further support a mechanism in which repulsive triplet excited-state PESs featuring a critical aryl-to-Ni LMCT lead to bond rupture. Structural control over excited-state PESs provides a rational approach to utilize photonic energy and leverage excited-state bond homolysis processes in synthetic chemistry.

Boryl Radical Activation of Benzylic C-OH Bond: Cross-Electrophile Coupling of Free Alcohols and CO2 via Photoredox Catalysis.

Abstract: A new strategy for the direct cleavage of the C(sp3)-OH bond has been developed via activation of free alcohols with neutral diphenyl boryl radical generated from sodium tetraphenylborate under mild visible light photoredox conditions. This strategy has been verified by cross-electrophile coupling of free alcohols and carbon dioxide for the synthesis of carboxylic acids. Direct transformation of a range of primary, secondary, and tertiary benzyl alcohols to acids has been achieved. Control experiments and computational studies indicate that activation of alcohols with neutral boryl radical undergoes homolysis of the C(sp3)-OH bond, generating alkyl radicals. After reducing the alkyl radical into carbon anion under photoredox conditions, the following carboxylation with CO2 affords the coupling product.

Visible-Light-Accelerated Copper-Catalyzed [3 + 2] Cycloaddition of N-Tosylcyclopropylamines with Alkynes/Alkenes.

Abstract: Copper-catalyzed [3 + 2] cycloadditions of N-tosylcyclopropylamine with alkynes and alkenes have been accomplished under visible light irradiation. The developed approach is compatible with a range of functionalities and allows the synthesis of diversified aminated cyclopentene and cyclopentane derivatives being relevant for drug synthesis. The protocol is operationally simple and economically affordable as it does not require any ligand, base, or additives. As the key step, the one-electron oxidation of the N-tosyl moiety by visible light-induced homolysis of a transient Cu(II)-tosylamide complex is proposed, providing a facile entry for N-centered radicals.

Designing radical chemistry by visible light-promoted homolysis

Abstract: The use of visible light to promote synthetic processes has been emerging rapidly in recent years. In the frame of eco-sustainable strategies involving the generation of reactive intermediates (especially radicals), the search for compounds able to directly undergo the photocleavage of a labile X–Y bond by using visible photons appears an intriguing alternative to the use of a colored photocatalyst. This review focuses on the recent efforts to design compounds having such X–Y moieties to be used in radical chemistry under photocatalyst-free conditions.

Azo-Crosslinked Double-Network Hydrogels Enabling Highly Efficient Mechanoradical Generation.

Abstract: Double-network (DN) hydrogels have recently been demonstrated to generate numerous radicals by the homolytic bond scission of the brittle first network under the influence of an external force. The mechanoradicals thus generated can be utilized to trigger polymerization inside the gels, resulting in significant mechanical and functional improvements to the material. Although the concentration of mechanoradicals in DN gels is much higher than that in single-network hydrogels, a further increase in the mechanoradical concentration in DN gels will widen their application. In the present work, we incorporate an azoalkane crosslinker into the first network of DN gels. Compared with the traditional crosslinker N,N'-methylenebis(acrylamide), the azoalkane crosslinker causes a decrease in the yield stress but significantly increases the mechanoradical concentration of DN gels after stretching. In the azoalkane-crosslinked DN gels, the concentration of mechanoradicals can reach a maximum of ∼220 μM, which is 5 times that of the traditional crosslinker. In addition, DN gels with the azoalkane crosslinker show a much higher energy efficiency for mechanoradical generation. Interestingly, DN gels crosslinked by a mixture of azoalkane crosslinker and traditional crosslinker also exhibit excellent radical generation performance. The increase in the mechanoradical concentration accelerates polymerization and can broaden the application range of force-responsive DN gels to biomedical devices and soft robots.

Decarboxylative tandem C-N coupling with nitroarenes via SH2 mechanism

Abstract: Aromatic tertiary amines are one of the most important classes of organic compounds in organic chemistry and drug discovery. It is difficult to efficiently construct tertiary amines from primary amines via classical nucleophilic substitution due to consecutive overalkylation. In this paper, we have developed a radical tandem C-N coupling strategy to efficiently construct aromatic tertiary amines from commercially available carboxylic acids and nitroarenes. A variety of aromatic tertiary amines can be furnished in good yields (up to 98%) with excellent functional group compatibility under mild reaction conditions. The use of two different carboxylic acids also allows for the concise synthesis of nonsymmetric aromatic tertiary amines in satisfactory yields. Mechanistic studies suggest the intermediacy of the arylamine-(TPP)Fe(III) species and might provide a possible evidence for an SH2 (bimolecular homolytic substitution) pathway in the critical C-N bond formation step.

Direct and Unified Access to Carbon Radicals from Aliphatic Alcohols by Cost-Efficient Titanium-Mediated Homolytic C-OH Bond Cleavage.

Abstract: Low-valent Ti-mediated homolytic C-O bond cleavage offers unified access to carbon radicals from ubiquitous non-activated tertiary, secondary, and even primary alcohols. In contrast to the representative Ti reagents, which were ineffective for this purpose, "TiCl 2 (cat)"/Zn (cat = catecholate) was found to be specifically active. This method was applied to the addition reactions of radicals to alkenes and exhibited high generality and yields. More than 50 combinations were examined. The excellent cost-efficiency and accessibility of "TiCl 2 (cat)"/Zn further enhance its applicability. Control experiments proved the presence of a carbon radical intermediate and excluded the pathway via alkyl chlorides. Further mechanistic study indicated that the 1:2 complex of alkoxide (R-O - ) and Ti(III) is an active species in the C-O cleavage.

Recent Advances in Type I Photoinitiators for Visible Light Induced Photopolymerization

Abstract: Photopolymerization and its application in the dental, three-dimensional (3D) printing, coating and electronic industry has become increasingly popular over the last decades. A huge variety of photoinitiators (PIs) and photoinitiating systems (PISs) have been developed that are able to generate reactive species, e. g. radicals, radical cations, and cations upon light absorption. In this Review, we focus on radical-generating Type I PIs which undergo homolytic cleavage after irradiation with visible light. The possibility to utilize electromagnetic irradiation above 400 nm for the initiation of polymerization reactions provides several advantages such as a lower energy demand and higher curing depths in pigmented reactive systems. Recent developments of PIs based on phosphorus and group 14 elements as well as other selected concepts for Type I visible light initiators are outlined and discussed within this review.

Nickel Catalysis via SH2 Homolytic Substitution: The Double Decarboxylative Cross-Coupling of Aliphatic Acids.

Abstract: Cross-coupling platforms are traditionally built around a sequence of closed-shell steps, such as oxidative addition, transmetalation, and reductive elimination. Herein, we describe a dual photo/nickel catalytic manifold that performs cross-coupling via a complementary sequence involving free radical generation, radical sorting via selective binding to a Ni(II) center, and bimolecular homolytic substitution (SH2) at a high-valent nickel-alkyl complex. This catalytic manifold enables the hitherto elusive cross-coupling of diverse aliphatic carboxylic acids to generate valuable C(sp3)-C(sp3)-products. Notably, the powerful SH2 mechanism provides general access to sterically encumbered quaternary carbon centers, addressing a long-standing challenge in fragment coupling chemistry.

Stimuli-Responsive Covalent Adaptable Hydrogels Based on Homolytic Bond Dissociation and Chain Transfer Reactions

Abstract: Covalent adaptable hydrogels containing dynamic covalent bonds are gaining significant interest based on their ability of stimuli-controlled reversible bond dissociation, structural reorganization, color change, and self-healing through covalent bond exchange or dissociation. Potential applications of such hydrogels have been explored in coatings, sealants, tissue adhesives, soft robotics, tissue engineering, and stimuli-responsive lithography. Stimuli-induced homolytic bond cleavage leads to the formation of radicals with the ability of recombination or transfer to induce bond exchange and color variation. The incorporation of such stimuli-responsive homolytically cleavable bonds in hydrogels can lead to stimuli-controlled plasticity, stress relaxation, self-healing, structural reorganization, mechanochromism, and mechanoluminescence. The resultant smart materials are interesting for different applications, ranging from patterning and shape-shifting, cell encapsulation and culturing, and protein binding to strain sensing and damage reporting. The recent progress in the preparation of covalently adaptable hydrogels based on stimuli-responsive homolytical bond dissociation and recombination or chain transfer will be discussed in this review. More specifically, the different types of chemistry that can be used for development of covalent adaptable hydrogels based on light-induced, temperature-induced, and mechanically induced homolytic bond dissociation will be discussed. Moreover, the applications of the resultant covalent adaptable hydrogels will be highlighted, focusing on stress sensing and damage reporting, tissue engineering, and self-healable hydrogels, as well as stimuli-controlled patterning and shape-shifting.

NHC induced radical formation via homolytic cleavage of B–B bonds and its role in organic reactions

Abstract: New borylation methodologies have been reported recently, wherein diboron(4) compounds apparently participate in free radical couplings via the homolytic cleavage of the B–B bond. We report herein that bis-NHC adducts of the type (NHC)2·B2(OR)4, which are thermally unstable and undergo intramolecular ring expansion reactions (RER), are sources of boryl radicals of the type NHC–BR2˙, exemplified by Me2ImMe·Bneop˙ 1a (Me2ImMe = 1,3,4,5-tetramethyl-imidazolin-2-ylidene, neop = neopentylglycolato), which are formed by homolytic B–B bond cleavage. Attempts to apply the boryl moiety 1a in a metal-free borylation reaction by suppressing the RER failed. However, based on these findings, a protocol was developed using Me2ImMe·B2pin23 for the transition metal- and additive-free boryl transfer to substituted aryl iodides and bromides giving aryl boronate esters in good yields. Analysis of the side products and further studies concerning the reaction mechanism revealed that radicals are likely involved. An aryl radical was trapped by TEMPO, an EPR resonance, which was suggestive of a boron-based radical, was detected in situ, and running the reaction in styrene led to the formation of polystyrene. The isolation of a boronium cation side product, [(Me2ImMe)2·Bpin]+I−7, demonstrated the fate of the second boryl moiety of B2pin2. Interestingly, Me2ImMe NHC reacts with aryl iodides and bromides generating radicals. A mechanism for the boryl radical transfer from Me2ImMe·B2pin23 to aryl iodides and bromides is proposed based on these experimental observations.

Coordination-Induced Bond Weakening.

Abstract: Coordination-induced bond weakening is a phenomenon wherein ligand X-H bond homolysis occurs in concert with the energetically favorable oxidation of a coordinating metal complex. The coupling of these two processes enables thermodynamically favorable proton-coupled electron transfer reductions to form weak bonds upon formal hydrogen atom transfer to substrates. Moreover, systems utilizing coordination-induced bond weakening have been shown to facilitate the dehydrogenation of feedstock molecules including water, ammonia, and primary alcohols under mild conditions. The formation of exceptionally weak substrate X-H bonds via small molecule homolysis is a powerful strategy in synthesis and has been shown to enable nitrogen fixation under mild conditions. Coordination-induced bond weakening has also been identified as an integral process in biophotosynthesis and has promising applications in renewable chemical fuel storage systems. This review presents a discussion of the advances made in the study of coordination-induced bond weakening to date. Because of the broad range of metal and ligand species implicated in coordination-induced bond weakening, each literature report is discussed individually and ordered by the identity of the low-valent metal. We then offer mechanistic insights into the basis of coordination-induced bond weakening and conclude with a discussion of opportunities for further research into the development and applications of coordination-induced bond weakening systems.

Formal Cycloadditions Driven by the Homolytic Opening of Strained, Saturated Ring Systems

Abstract: Abstract The field of strain‐driven, radical formal cycloadditions is experiencing a surge in activity motivated by a renaissance in free radical chemistry and growing demand for sp3‐rich ring systems. The former has been driven in large part by the rise of photoredox catalysis, and the latter by adoption of the “Escape from Flatland” concept in medicinal chemistry. In the years since these broader trends emerged, dozens of formal cycloadditions, including catalytic, asymmetric variants, have been developed that operate via radical mechanisms. While cyclopropanes have been studied most extensively, a variety of strained ring systems are amenable to the design of analogous reactions. Many of these processes generate lucrative, functionally decorated sp3‐rich ring systems that are difficult to access by other means. Herein, we summarize recent efforts in this area and analyze the state of the field.

How Do Metalloproteins Tame the Fenton Reaction and Utilize •OH Radicals in Constructive Manners?

Abstract: ConspectusThis Account describes the manner whereby nature controls the Fenton-type reaction of O-O homolysis of hydrogen peroxide and harnesses it to carry out various useful oxidative transformations in metalloenzymes. H2O2 acts as the cosubstrate for the heme-dependent peroxidases, P450BM3, P450SPα, P450BSβ, and the P450 decarboxylase OleT, as well as the nonheme enzymes HppE and the copper-dependent lytic polysaccharide monooxygenases (LPMOs). Whereas heme peroxidases use the Poulos-Kraut heterolytic mechanism for H2O2 activation, some heme enzymes prefer the alternative Fenton-type mechanism, which produces •OH radical intermediates. The fate of the •OH radical is controlled by the protein environment, using tight H-bonding networks around H2O2. The so-generated •OH radical is constrained by the surrounding H-bonding interactions, the orientation of which is targeted to perform H-abstraction from the Fe(III)-OH group and thereby leading to the formation of the active species, called Compound I (Cpd I), Por+•Fe(IV)═O, which performs oxidation of the substrate. Alternatively, for the nonheme HppE enzyme, the O-O homolysis catalyzed by the resting state Fe(II) generates an Fe(III)-OH species that effectively constrains the •OH radical species by a tight H-bonding network. The so-formed H-bonded •OH radical acts directly as the oxidant, since it is oriented to perform H-abstraction from the C-H bond of the substrate (S)-2-HPP. The Fenton-type H2O2 activation is strongly suggested by computations to occur also in copper-dependent LPMOs and pMMO. In LPMOs, the Cu(I)-catalyzed O-O homolysis of the H2O2 cosubstrate generates an •OH radical that abstracts a hydrogen atom from Cu(II)-OH and forms thereby the active species of the enzyme, Cu(II)-O•. Such Fenton-type O-O activation can be shared by both the O2-dependent activations of LPMOs and pMMOs, in which the O2 cosubstrate may be reduced to H2O2 by external reductants. Our studies show that, generally, the H2O2 activation is highly dependent on the protein environment, as well as on the presence/absence of substrates. Since H2O2 is a highly flexible and hydrophilic molecule, the absence of suitable substrates may lead to unproductive binding or even to the release of H2O2 from the active site, as has been suggested in P450cam and LPMOs, whereas the presence of the substrate seems to play a role in steering a Fenton-type H2O2 activation. In the absence of a substrate, the hydrophilic active site of P450BM3 disfavors the binding and activation of H2O2 and protects thereby the enzyme from the damage by the Fenton reaction. Due to the distinct coordination and reaction environment, the Fenton-type H2O2 activation mechanism by enzymes differs from the reaction in synthetic systems. In nonenzymatic reactions, the H-bonding networks are quite dynamic and flexible and the reactivity of H2O2 is not strategically constrained as in the enzymatic environment. As such, our Account describes the controlled Fenton-type mechanism in metalloenzymes, and the role of the protein environment in constraining the •OH radical against oxidative damage, while directing it to perform useful oxidative transformations.

Visible-Light-Induced 1,6-Enynes Triggered C-Br Bond Homolysis of Bromomalonates: Solvent-Controlled Divergent Synthesis of Carbonylated and Hydroxylated Benzofurans.

Abstract: Visible-light-induced 1,6-enyne-triggered C-Br bond homolysis of bromomalonates has been developed. This transition-metal-free, photocatalyst-free, and oxidant- and additive-free protocol affords an efficient approach for divergent synthesis of carbonylated and hydroxylated benzofurans from 1,6-enynes and bromomalonates under mild conditions. Significantly, mechanistic studies reveal that the homolysis of C-Br bonds appears to experience an energy-transfer pathway, and the atom-transfer radical addition products are the key intermediates to generate carbonylated and hydroxylated benzofurans.

New Approach to the Detection of Short-Lived Radical Intermediates

Abstract: We report a new general method for trapping short-lived radicals, based on a homolytic substitution reaction SH2′. This departure from conventional radical trapping by addition or radical–radical cross-coupling results in high sensitivity, detailed structural information, and general applicability of the new approach. The radical traps in this method are terminal alkenes possessing a nitroxide leaving group (e.g., allyl-TEMPO derivatives). The trapping process thus yields stable products which can be stored and subsequently analyzed by mass spectrometry (MS) supported by well-established techniques such as isotope exchange, tandem MS, and high-performance liquid chromatography-MS. The new method was applied to a range of model radical reactions in both liquid and gas phases including a photoredox-catalyzed thiol–ene reaction and alkene ozonolysis. An unprecedented range of radical intermediates was observed in complex reaction mixtures, offering new mechanistic insights. Gas-phase radicals can be detected at concentrations relevant to atmospheric chemistry.

Theoretical Study on Nitrobenzene Hydrogenation by N-Doped Carbon-Supported Late Transition Metal Single-Atom Catalysts

Abstract: A density functional theory (DFT) study was performed to investigate the activities of 12 late transition metal single-atom-supported nitrogen-doped carbon-based catalysts (M1-N4/C SACs) nitrobenzene hydrogenation. Three different dihydrogen (H2) dissociation mechanisms are proposed: homolytic cleavage at the metal (M) site, heterolytic cleavage at M–N sites, and heterolytic cleavage at M–N–C sites. The coadsorption of nitrobenzene (PhNO2) and H2 was proposed, and the effect of charge change of hydrogen atoms caused by the coverage of PhNO2 on the H2 dissociation activity was revealed. Six M1–N4/C SACs (M = Ru, Os, Fe, Ag, Ir, Rh) with a potentially high activity of H2 dissociation were screened. Then, the two crucial steps, H2 dissociation and the second N–O bond breaking (PhNOH* + H* → PhN* + H2O), were compared. The obtained results indicate that different M1–N4/C SACs might have different rate-determining steps for nitrobenzene hydrogenation and that Ru1–N4/C SAC could be one of the most promising catalysts with good catalytic activities for nitrobenzene hydrogenation.

Catalytic Enantioselective Synthesis of γ-Lactams with β-Quaternary Centers via Merging of C-C Activation and Sulfonyl Radical Migration.

Abstract: Transition-metal-catalyzed C-C activation has become synthetically valuable; however, it rarely involves single-electron downstream processes. To expand the repertoire of C-C activation, here we describe the discovery of a Rh-catalyzed enantioselective C-C activation involving migration of a sulfonyl radical. This reaction directly transforms cyclobutanones containing a sulfonamide-tethered 1,3-diene moiety into γ-lactams containing a β-quaternary center with excellent enantioselectivity. This unusual process involves cleavage of C-C and N-S bonds and subsequent formation of C-N and C-S bonds. The reaction also exhibits broad functional group tolerance and a good substrate scope. A combined experimental and computational mechanistic study suggested that the reaction goes through a Rh(I)-mediated oxidative addition into the cyclobutanone C-C bond followed by a Rh(III)-triggered N-S bond homolysis and sulfonyl radical migration.