Amidyl Radical Directed γ-C(sp3)−H Functionalization with Silyl Enol Ethers via Photoredox Catalysis

Herein we reported an efficient photoredox-catalyzed reaction for site-selective C(sp³)−H functionalization of carboxamides with silyl enol ethers as radical acceptors. The reaction proceeded through amidyl radical-directed 1,5-hydrogen atom transfer (1,5-HAT) and C(sp³)−C(sp³) bond formation via radical addition of silyl enol ethers. The process features mild conditions and high functional-group tolerance, allowing the preparation of a series of carboxamides with pendant carbonyl moieties.     

σ,π-Conjugation in organomercurial systems

Two series of compounds LHgL′ are described. In series I, L = L′ = organic radical with an oxo group in position 2 or L′ = Cl, in series II, L = L′ = allylic radical or L′ = Cl. Some compounds possess chemical properties of conjugated systems (IA, IIA), while others do not possess such properties (IB, IIB). The J¹³C¹⁹⁹Hg) coupling constants and chemical shifts in ¹³C NMR spectra, the integral intensities of multiple bond vibrations in Raman spectra, the half-wave reduction potentials and the resonance energies in mass spectra of the negative ions are compared. The main contribution to the observed differences between compounds A and B is made by interaction of the CHg σ-bond with the π-system (σ, π-conjugation).     

Trapping of photogenerated group IV radicals by TEMPO: Potential new organometallic initiators for “living” free radical polymerization

A series of trialkyl and triaryl organometallic radicals from group IV generated by hydrogen abstraction by tert‐butoxyl radical from the parent hydrides have been examined using laser flash photolysis. The rate constants for the trapping of the metal‐centered radicals by the persistent radical TEMPO were measured and were found to be large and similar to those of the carbon‐centered radical systems, yet below the diffusion controlled limit. The metal‐centered radicals were found to be efficiently trapped by TEMPO and would appear to be candidates suitable for “living” free radical polymerization similar to carbon analogue stoichiometric initiators. The radical trapping rate constants for the trialkyl series (M = Si, Ge, Sn) were found to be 8.9 × 10⁸ M⁻¹ s⁻¹ (M = Si), 7.2 × 10⁸ M⁻¹ s⁻¹ (M = Ge), and 6.2 × 10⁸ M⁻¹ s⁻¹ (M = Sn), respectively. The triaryl (Ph₃M•) series gave slightly slower rates of 1.6 × 10⁸ M⁻¹ s⁻¹ (M = Si), 3.4 × 10⁸ M⁻¹ s⁻¹ (M = Ge), and 1.9 × 10⁷ M⁻¹ s⁻¹ (M = Sn), respectively. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 238–244, 2000     

Effect of non-planarity on the spin distribution in the radical anions containing the stilbene or the azobenzene π-system: An ESR and ENDOR Study

The radical anions of 5H-dibenzo[a,d]cycloheptene ( 9 ), 5 H-dibenzo[c,f][1,2]diazepine ( 10 ), 5,6-dihydrodibenzo[a,e]cyclooctene ( 11 ), 5,6-dihydrodibenzo[c,g][1,2]diazocine ( 12 ), and (E)-2,2,5,5-tetramethyl-3,4-diphenylhex-3-ene ( 13 ) were characterized by ESR and ENDOR spectroscopy. Their hyperfine data were compared with those previously reported for radical anions also containing the stilbene or the azobenzene π-system. Whereas the π-spin distribution in the radical anions of the stilbene series is only moderately sensitive to deviations of the π-system from planarity, the radical anions of the azobenzene series respond to steric strain by shifting the π-spin population from the benzene rings to the azo group. This finding is impressively demonstrated by the similar hyperfine data for 9 ^{· ?} and 11 ^{· ?} which contrast with the strongly highly hindered 13 ^{· ?}. A. plausible interpretation is readily provided by the electron affinities of the constituent π-moieties in stilbene and azobenzene. While those of benzene and ethene are both comparatively low, the azo group has a considerably higher electron affinity.     

Regio-and stereoselectivity in the halogenation of methyl tricyclo[4.1.0.02,7]heptane-1-carboxylate

Conjugate halogenation of methyl tricyclo[4.1.0.0^2,7]heptane-1-carboxylate by the action of N-iodoand N-bromosuccinimides in the presence of halide ions occurs exclusively at the central bicyclobutane C¹–C⁷ bond via electrophilic attack on the C¹ atom, leading to endo,syn-adducts of the norpinane series. Reactions of the title compound with iodine, dibromotetrachloroethane, and (dichloro-λ³-iodanyl)benzene give not only the corresponding 6,7-endo,syn-dihalonorpinane but also its epimer at C⁶, indicating radical mechanism of the halogenation. The regio-and stereoselectivity observed in these ionic and radical reactions are discussed in terms of the results of nonempirical MP2/STO-3G calculations of appropriate cationic and radical intermediates.     

Synthesis and Antioxidant Activities of Novel 4,4′‐Arylmethylene‐bis(1H‐pyrazole‐5‐ol)s from Lignin

A series of novel bispyrazoles joined by arylmethylene at C‐4 position were synthesized with aromatic aldehydes obtained from lignin and screened for their in vitro antioxidant activities by N,N‐diphenyl‐N′‐picrylhydrazyl (DPPH) and 2,2′‐azino‐bis(3‐ethylenzothiazoline‐sulphonic acid) diammonium salt (ABTS⁺) radical scavenging assays. All of these compounds exhibited good DPPH and ABST⁺ radical scavenging activities as compared to the standard, Trolox, which suggested their potential as promising agents for curing tumors or other free radical‐related diseases.     

Donor–Acceptor Complex Enables Alkoxyl Radical Generation for Metal‐Free C(sp3)–C(sp3) Cleavage and Allylation/Alkenylation

The alkoxyl radical is an essential and prevalent reactive intermediate for chemical and biological studies. Here we report the first donor–acceptor complex‐enabled alkoxyl radical generation under metal‐free reaction conditions induced by visible light. Hantzsch ester forms the key donor–acceptor complex with N ‐alkoxyl derivatives, which is elucidated by a series of spectrometry and mechanistic experiments. Selective C(sp³)‐C(sp³) bond cleavage and allylation/alkenylation is demonstrated for the first time using this photocatalyst‐free approach with linear primary, secondary, and tertiary alkoxyl radicals.     

Oxime Ether Radical Cations Stabilized by N‐Heterocyclic Carbenes

N‐heterocyclic carbene (NHC) nitric oxide (NHCNO) radicals, which can be regarded as iminoxyl radicals stabilized by NHCs, were found to react with a series of silyl and alkyl triflates to generate the corresponding oxime ether radical cations. The structures of the resulting oxime ether radical cations were determined by X‐ray crystallography, along with EPR and computational analysis. In contrast, lutidinium triflate produced a 1:1 mixture of [NHCNO⁺][OTf^?] and [NHCNHOH⁺][OTf^?] upon the reaction with NHCNO. This study adds an important example of stable singlet carbenes for stabilizing main‐group radicals because of their π‐conjugating effect, the synthesis and structures of which have not been reported previously.     

Steady-state γ-radiolysis of aqueous methyl ethyl ketone (2-butanone) under postulated nuclear reactor accident conditions

The steady-state γ-radiolysis of aqueous solutions containing 1×10⁻³ mol dm⁻³ methyl ethyl ketone (MEK) has been studied at a dose rate of 0.12 Gy s⁻¹, 25°C and an initial pH of 10. Experiments were conducted in air-, Ar- or N₂O-purged aqueous solutions, or in Ar-purged solutions with added tert-butanol. MEK, its radiolytic products, and the change in pH resulting from MEK decomposition were analysed as a function of time (or total absorbed dose). The main initial step for the radiolytic decomposition of MEK is the H abstraction from MEK by OH, produced by γ-radiolysis of water, to form MEK radical. In the absence of O, the main decay path of the MEK radical appears to be dimerization to , -dimethyl-2,5-hexanedione. In the presence of oxygen, the MEK radical reacts primarily with O to form the MEK peroxyl radical. This radical ultimately results in a series of progressively smaller oxidation products. The formation of organic acids, and eventually CO₂, reduces the pH of the solution. This paper presents the experimental data and proposes the MEK decay kinetics and mechanism.     

Spin-Distribution-Directed Regioselective Substitution Strategy for Highly Stable Olympicenyl Radicals

The synthesis of bench-stable conjugated π-radicals is challenging owing to the lack of modular approaches, which greatly hampers their practical material screens and applications. Here, we demonstrate a spin-distribution-directed regioselective substitution strategy to introduce substituents into the specific positions of an olympicenyl radical in a stepwise manner, resulting in a series of highly stable radical species. The substituents can also adjust the crystal packing by means of steric and electronic factors, enabling the changing from a π-dimer to a pseudo-one-dimensional chain. The first single crystal organic field-effect transistor device based on a graphenic radical is fabricated in air, showing a hole mobility of up to 0.021 cm² V⁻¹ s⁻¹ and excellent device stability. This approach may be generalized to diverse spin-delocalized open-shell organic radicals.     

SYNTHESIS AND POLYMERIZATION OF 2-OXO-3-METHYLENE-5, 6-DIPHENYL-1,4-DIOXAN

A new cyclic monomer, 2-oxo-3-methylene-5, 6-diphenyl-1, 4-dioxan, was synthesized. Thestructure of the intermediates and the monomer were determined by IR,~1H NMR,~(13)C NMR andelemental analysis. This new monomer is different from other cyclic monomers in this series,it isa solid (mp 108--109℃)and not very reactive, but still can undergo free radical ring-openingpolymerization. The free radical polymerization was carried out at 130℃. The structure of theresulting polymer was discussed and charaterized by IR, ~1H NMR, ~(13)C NMR and elementalanalysis. The molecular weight of the polymer was estimated by viscosity determination.     

Mechanistic aspects of the bromination of 10-substituted phenothiazines

The addition of 1 and 2 molar equivalents of bromine to a series of 10-alkylphenothiazines, 1a-d (methyl, ethyl, n-propyl, and isopropyl, respectively), yields the corresponding 3-bromo- and 3,7-dibromo-10-alkylphenothiazines ( 11a-d and 12a-d , respectively). Evidence which supports the typical clectrophilic aromatic substitution mechanism is presented. Radical cations ( 12a-d^.+ ) arc produced when 12a-d are treated with 1 or 2 molar equivalents of bromine. Upon boiling in acetic acid these radical cations are converted predominantly to 1,3,7,9-lelrabromophenothiazine ( 5 ) and the parent 3,7-dibromo-10-alkylphenothiazine ( 12a-d ) with the evolution of hydrogen bromide. The 10-methyl radical ( 12a ) gives, in addition, 1,3,7-tribromo-10-methylphenothiazine ( 15 ). A mechanism if proposed for these reactions in which initial dealkylution of 12b-d^.+ to 3.7-dibromophenothiazine radical cation ( 13 ) occurs followed by reduction of 13^.+ by bromide ion to parent 3,7-dibromophenothiazine ( 13 ). Subsequent bromination of 13 by molecular bromine produced in the previous redox reaction yields 1,3,7-tribromo-( 14 ) and 1,3,7,9-tetra-bromo-( 5 ) phenothiazines. The small size of the methyl group allows 12a to be brominated at the 1-position prior to dealkylation. In addition to undergoing bromination at the 3- and 7-position, 10-isopropylphenothiazine ( 1d ) is oxidized to the radical cation 12e^.+ when treated with bromine. 10-Benzylphenothiazine ( 1e ), however, undergoes oxidation to radical cation 1e^.+ exclusively. This radical cation debenzylates readily at room temperature and is converted finally into phenothiazine.     

Radical cation salt induced tandem cyclization between anilines and N-vinyl amides: synthesis of 2-methyl-4-anilino-1,2,3,4-tetrahydroquinoline derivatives

A tandem cyclization of imines with N-vinyllactams induced by TBPA⁺ was investigated, and a series of 2-methyl-4-anilino-1,2,3,4-tetrahydroquinolines were synthesized based on a domino process in which N-vinyllactams serve as an acetaldehyde surrogate. A single electron transfer mechanism was proposed and radical cation salt acts as both a Lewis acid and one electron oxidant to induce such transformation.     

Structure,spectroscopy and magnetism of 1,4-dihydro-1,4-diazine radical cations: Exceptionally stable intermediates related to methylviologen and flavosemiquinone radicals

-1,4-Dialkyl-1,4-dihydro-1,4-diazine radical cations 1–3 have been established in recent years as unusually stable intermediates of corresponding two-step redox systems. The stability is evident from large comproportionation constants K_c > 10¹² and from the isolability of persistent radical cation salts with counter anions such as Br^-, I^-, I₃ ^-, PF₆ ^-, BPh4-, or (TCNQ₂)^-. The structures of several crystalline derivatives have been determined, showing planar π systems and, in one instance, an anion-dependent tendency to form π/π dimers. Effects of dimerization are also evident from comparative magnetic susceptibility measurements of 1,4-diethyl-1,4-dihydroquinoxalinium iodide and tetraphenylborate. UV/Vis absorption spectra of the radical cations have been determined and interpreted with the help of molecular orbital calculations. The most simple member of the series, 1,4-diethyl-1,4-dihydropyrazinum radical cation 1, exhibits a long wavelength forbidden band (²B_1u → ²A_u) with a conspicuous vibrational fine structure. The results obtained for the small but very stable new radical cations 1 and 2 provide clues to the stability of flavosemiquinone oxidation states in pertinent oxidoreductase enzymes and show ways to new components for the design of materials with anisotropic physical properties.     

Small ring compounds—XXX : Homolytical aromatic substitution and hydrogen abstraction reaction with cyclopropyl radical

Homolytic aromatic substitution and hydrogen abstraction reactions with cyclopropyl radical were carried out to determine the reactivity and ionic character of cyclopropyl radical by examination of the orientation effect, partial rate factor and influence of substituents. By thermal decomposition of biscyclopropaneformyl peroxide in a series of substituted benzenes, the corresponding cyclopropylated benzene derivatives (the mixture of ortho, meta and para isomers) were obtained in moderate yield. In view of the orientation effect and the partial rate factor, the cyclopropyl radical seems to be fairly free from polar effect, and to resemble the phenyl radical more than the common alkyl radical although the cyclopropyl radical has a slightly higher reactivity than the phenyl radical. The relative reactivity of the 2-phenylcyclopropyl radical in the hydrogen abstraction reaction toward the benzylic position of ring-substituted toluenes gave good Hammett's correlation with the slope of + 0·20 suggesting little ionic character in the transition state. This result was in good agreement with the conclusion obtained from homolytic aromatic substitution reaction and with the chemical reactivity to be expected from the non-planar nearly sp²-hybridized conformation of the cyclopropyl radical.     

Electron ionization mass spectrometric study of substituted alloxazine‐5‐oxides and iso‐alloxazine‐5‐oxide

The fragmentation pathways in electron ionization (EI) mass spectra of a series of new N(5)‐oxides of alloxazines and iso‐alloxazine are presented, and compared with those of substituted alloxazines and iso‐alloxazine. The EI mass spectra of these compounds showed characteristic fragmentation pathways A, B and C, started by the ejection of atomic oxygen, a HNCO molecule and an OH ^. radical, respectively. On the basis of B/E and B²/E spectra, the mechanism of elimination of the OH ^. radical is discussed. The influence of the methyl substituent in the benzene ring of alloxazine on the mass fragmentation pathways is described. Copyright © 2009 John Wiley & Sons, Ltd.     

Molecular ions of 3,3′-bi(2-R-5,5-dimethyl-4-oxopyrrolinylidene) 1,1′-dioxides

The electrochemical reduction of 3,3′-bi(2-R-5,5-dimethyl-4-oxopyrrolinylidene) 1,1′-dioxides (R = CF₃, Me, Ph, Bu^t), which are cyclic dinitrons with conjugated C=C bond, in acetonitrile is an EE process producing stable radical anions and dianions, whereas the electrochemical oxidation is an EEC (R = Me, Ph) or EE process (R = Bu^t) with formation of radical cations (except for the case of R = CF₃) and dications (R = Bu^t) stable under standard conditions. Radical cations of the dioxides with R = Me, Ph, and Bu^t and radical anions of the whole series of the compounds studied, including R = CF₃, were characterized by ESR spectroscopy combined with electrochemical measurements and quantum-chemical calculations. The electrochemical behavior of the Bu^t-substituted dinitron is unique: the EE processes in the region of negative and positive potentials with formation of the dianion, radical anion, radical cation, and dication stable at T = 298 K were observed for the first time within one cycle of potential sweep in the CV curve measured in MeCN. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1148–1154, May, 2005.     

Photoionization of OH in the region 750–950 Å

The relative photoionization cross section of the hydroxyl radical (OH), was determined in the wavelength region from 750 to 950 A at a resolution of 0.07–0.23 A. Numerous new electronic transitions are observed and several members of a Rydberg series converging to OH⁺ a¹ Δ tentatively are assigned.     

Catalytic Hydrogenation of α,β-Epoxyketones to β-Hydroxyketones with Two Sulfinyl Analogues of Coenzyme NADH Models

An efficient method for the selective hydrogenation of a series of α,β-epoxyketones to β-hydroxyketones using catalytic amount of two sulfinyl analogues of NAD^＋ model compounds is reported. The lack of any diastereoselectivity for the formation of β-hydroxyketones with optically pure sulfinyl analogue of NAD^＋ model supports the radical mechanism proposed previously.     

Coordination Complexes of a Neutral 1,2,4‐Benzotriazinyl Radical Ligand: Synthesis,Molecular and Electronic Structures,and Magnetic Properties

A series of d‐block metal complexes of the recently reported coordinating neutral radical ligand 1‐phenyl‐3‐(pyrid‐2‐yl)‐1,4‐dihydro‐1,2,4‐benzotriazin‐4‐yl ( 1 ) was synthesized. The investigated systems contain the benzotriazinyl radical 1 coordinated to a divalent metal cation, Mn^II, Fe^II, Co^II, or Ni^II, with 1,1,1,5,5,5‐hexafluoroacetylacetonato (hfac) as the auxiliary ligand of choice. The synthesized complexes were fully characterized by single‐crystal X‐ray diffraction, magnetic susceptibility measurements, and electronic structure calculations. The complexes [Mn( 1 )(hfac)₂] and [Fe( 1 )(hfac)₂] displayed antiferromagnetic coupling between the unpaired electrons of the ligand and the metal cation, whereas the interaction was found to be ferromagnetic in the analogous Ni^II complex [Ni( 1 )(hfac)₂]. The magnetic properties of the complex [Co( 1 )(hfac)₂] were difficult to interpret owing to significant spin–orbit coupling inherent to octahedral high‐spin Co^II metal ion. As a whole, the reported data clearly demonstrated the favorable coordinating properties of the radical 1 , which, together with its stability and structural tunability, make it an excellent new building block for establishing more complex metal–radical architectures with interesting magnetic properties.