J. Lusztyk's research while affiliated with University of Duisburg-Essen and other places

Publications (175)

Article
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Article
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Article
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Article
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Article
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Article
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Article
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Article
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Article
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Article
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Article
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Article
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Article
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Article
Laser flash photolysis (LFP) techniques with detection in the infrared and in UV-visible regions of the spectrum have been used in combination with detailed product studies to assess solvent effects on the hydrogen abstraction and beta-scission reactions of cumyloxyl radicals. The variation in the ratio of the products of these two competing proces...
Article
Abstract: The rate of hydrogen-atom abstraction from XH by a radical, Y, can be solvent-dependent. In many cases, the kinetic solvent effect (KSE) is directly related to hydrogen-bonding interactions between XH and the solvent. The relative hydrogen-bond acceptor (HBA) properties of solvents are given by constants of Abraham et al. (Abraham, M. H.;...
Article
The thermal decomposition of bis(4-carboxybenzyl)hyponitrite (SOTS-1) in aerated water under physiological conditions has previously been shown to give the superoxide radical anion in a yield of 40 mol % (Ingold, K. U.; et al. J. Am. Chem. Soc. 1997, 119, 12364). The absolute kinetics of the elementary reactions involved in the cascade of events le...
Article
The effect of methoxy substitution on the abstraction of the phenolic hydrogen atom involved in intramolecular hydrogen bonding by tert-butoxyl and cumyloxyl radicals has been investigated by laser flash photolysis. Also transition state calculations for methoxyl radical and 2-methoxyphenol have been carried out by a density functional theory (DFT)...
Article
The preparations of the five ferrocenoyl-oligopeptides, FcProOBzl (1), FcPro2OBzl (2), FcPro3OBzl (3), FcPro4OBzl (4) and FcPro2PheOBzl (5) are described. Crystallographic studies show that the Fc-oligoprolines 1–4 adopt a helical polyproline II structure having all prolines in a mutually trans-conformation. This structure is maintained...
Article
Using competition kinetic methodology, rate constants for cyclizations of a series of hydrofluorocarbon (HFC) and ether 5-hexenyl, 6-heptenyl, and 7-octenyl radicals have been determined. Remarkably large rate constants (> 107 s-1) have been observed for 6-exo-cyclizations of 1,1,2,2-tetrafluoro- and 1,1,2,2,3,3,4,4,-octafluoro-6-heptenyl radicals...
Article
The first estimates of the lifetimes of the 2-propyl cation (4a), cyclobutonium ion (4b), cyclopropylethyl cation (4c), and 2-adamantyl cation (4d) in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), trifluoroethanol (TFE), and acetonitrile solvents have been determined using electrophilic aromatic addition to 1,3,5-trimethoxybenzene as a kinetic probe re...
Article
Laser flash photolysis (UV-LFP, 308 nm) of suitably substituted oxadiazolines leads to cyclohexylidene (14a), 4-tert-butyl-cyclohexylidene (14b), 2-trifluoromethylcyclohexylidene (14d), 8-aza-8-methyl[3.2.1]oct-3-ylidene (14e), diethylcarbene (14f), and ethyl(methyl)carbene (14h). Carbene intermediates were inferred from the products of steady stat...
Article
Laser flash photolysis (UV-LFP) studies of benzylchlorodiazirine (1a), phenylchlorodiazirine (1b), phenylmethoxydiazirine (1c), 2,2-dimethoxy-5,5-dimethyl-Δ3-1,3,4-oxadiazoline (6a), 3,4-diaza-2,2-dimethoxy-1-oxa[4.3]spirooct-3-ene (6b), 5‘,5‘-dimethoxyspiro[adamantane]-2,2‘-[Δ3-1,3,4-oxadiazoline] (6c), and diazofluorene (DAF) in the presence of o...
Article
The title ketene 2 has been generated by laser flash photolysis and observed in solution for the first time, using time-resolved infrared spectroscopy. The kinetics of the reactivity of 2 with H2O, MeOH, and Et2NH with relative reactivities of 1.0, 2.0, and 73 have been measured. These are the first direct measurements of the reactivities of a kete...
Article
Two of us (MSP and SM) previously reported [S. Morgan, J.E. Jackson, M.S. Platz, J. Am. Chem. Soc. 113 (1991) 2782] that adamantylidene (Ad:) reacts with thiophene to form an ylide which absorbs at 320 nm. It was concluded that Ad: has a lifetime of 2.2 μs in benzene and rather low absolute rate constants of reaction with thiophene and pyridine (1....
Article
Laser flash photolysis with time-resolved infrared detection of transients (LFP-TRIR) has been used to study the IR spectroscopy and reactivity of a number of substituted ketenes, prepared by the 308-nm photolysis of α-diazocarbonyl precursors in acetonitrile solution at room temperature. The correlation of the experimental ketene asymmetric stretc...
Article
The interconversion of cyclobutene-1,2-diones (1) and 1,2-bisketenes (RCCO)2 (2) has been surveyed for different combinations of substituents R = H, Me, t-Bu, Ph, Me3Si, CN, Cl, Br, R1O, alkynyl, and PhS. The bisketenes 2 have been generated by flash photolysis, and the kinetics of their conversion to 1 have been studied by time-resolved infrared a...
Article
The interconversion of cyclobutene-1,2-diones(1) and 1,2-bisketenes (RC=C=O)(2)(2) has been surveyed for different combinations of substituents R=H, Me, t-Bu, Ph, Me3Si, CN, Cl, Br, (RO)-O-1, alkyl, and PhS. The bisketenes 2 have been generated by flash photolysis, and the kinetics of their conversion to 1 have been studied by time-resolved infrare...
Article
Three independent methods have been employed to estimate the rate constant, k1, for ring-opening of the 2-cyclopropyl-2-propyl radical, 1, at room temperature. These three estimates are based on chemical trapping of 1 and the ring-opened 4-methylpent-3-ene-1-yl radical by thiophenol (k1 = (1.65 ± 0.41) × 107 M-1 s-1), 9-azabicyclo[3.3.1]nonane-N-ox...
Article
The ketene derived from diazoquinone 5 can be readily detected by laser photolysis techniques with IR detection and its behavior agrees with that observed with more conventional UV-visible detection. The ketene reacts with amines (e.g. k ∼7 × 107 M−1 s−1 for diethylamine) to give ylides (yielding amides as final products) that absorb in the 300–340...
Article
Absolute rate constants for hydrogen abstraction from n-Bu3SnH by a number of partially-fluorinated and fully fluorinated n-alkyl radicals have been measured. The C-H and C-C bond dissociation energies for a number of pertinent hydrofluorocarbons have been calculated by DFT. The rate data are compared with those for addition of the same radicals to...
Article
A series of ester-protected amino acids were coupled to ferrocenecarboxylic acid (1) using the DCC/HOBt protocol to give ferrocenoyl N-amino acids (amino acid = Glu(OBz)(2) (2a), Gly(OEt) (2b), Pro(OBz) (2c), Cys(SBz)OMe (2d), Ala(OBz) (2e), Tyr(OBz) (2f), Phe(OBz) (2g)). All products were fully characterized. The intermediate hydroxybenzotriazole...
Chapter
Summary This document is part of Subvolume D1 ‘Alkoxyl, Carbonyloxyl, Phenoxyl, and Related Radicals’ of Volume 18 ‘Radical Reaction Rates in Liquids’ of Landolt-Börnstein - Group II Molecules and Radicals.
Chapter
Summary This document is part of Subvolume D1 ‘Alkoxyl, Carbonyloxyl, Phenoxyl, and Related Radicals’ of Volume 18 ‘Radical Reaction Rates in Liquids’ of Landolt-Börnstein - Group II Molecules and Radicals.
Chapter
Summary This document is part of Subvolume D1 ‘Alkoxyl, Carbonyloxyl, Phenoxyl, and Related Radicals’ of Volume 18 ‘Radical Reaction Rates in Liquids’ of Landolt-Börnstein - Group II Molecules and Radicals.
Chapter
Summary This document is part of Subvolume D1 ‘Alkoxyl, Carbonyloxyl, Phenoxyl, and Related Radicals’ of Volume 18 ‘Radical Reaction Rates in Liquids’ of Landolt-Börnstein - Group II Molecules and Radicals.
Chapter
Summary This document is part of Subvolume D1 ‘Alkoxyl, Carbonyloxyl, Phenoxyl, and Related Radicals’ of Volume 18 ‘Radical Reaction Rates in Liquids’ of Landolt-Börnstein - Group II Molecules and Radicals.
Chapter
Summary This document is part of Subvolume D1 ‘Alkoxyl, Carbonyloxyl, Phenoxyl, and Related Radicals’ of Volume 18 ‘Radical Reaction Rates in Liquids’ of Landolt-Börnstein - Group II Molecules and Radicals.
Chapter
Summary This document is part of Subvolume D1 ‘Alkoxyl, Carbonyloxyl, Phenoxyl, and Related Radicals’ of Volume 18 ‘Radical Reaction Rates in Liquids’ of Landolt-Börnstein - Group II Molecules and Radicals.
Chapter
Summary This document is part of Subvolume D1 ‘Alkoxyl, Carbonyloxyl, Phenoxyl, and Related Radicals’ of Volume 18 ‘Radical Reaction Rates in Liquids’ of Landolt-Börnstein - Group II Molecules and Radicals.
Chapter
Summary This document is part of Subvolume D1 ‘Alkoxyl, Carbonyloxyl, Phenoxyl, and Related Radicals’ of Volume 18 ‘Radical Reaction Rates in Liquids’ of Landolt-Börnstein - Group II Molecules and Radicals.
Chapter
Summary This document is part of Subvolume D1 ‘Alkoxyl, Carbonyloxyl, Phenoxyl, and Related Radicals’ of Volume 18 ‘Radical Reaction Rates in Liquids’ of Landolt-Börnstein - Group II Molecules and Radicals.
Chapter
Summary This document is part of Subvolume D1 ‘Alkoxyl, Carbonyloxyl, Phenoxyl, and Related Radicals’ of Volume 18 ‘Radical Reaction Rates in Liquids’ of Landolt-Börnstein - Group II Molecules and Radicals.
Chapter
Summary This document is part of Subvolume D1 ‘Alkoxyl, Carbonyloxyl, Phenoxyl, and Related Radicals’ of Volume 18 ‘Radical Reaction Rates in Liquids’ of Landolt-Börnstein - Group II Molecules and Radicals.
Chapter
Summary This document is part of Subvolume D1 ‘Alkoxyl, Carbonyloxyl, Phenoxyl, and Related Radicals’ of Volume 18 ‘Radical Reaction Rates in Liquids’ of Landolt-Börnstein - Group II Molecules and Radicals.
Article
Abstract: Laser flash photolysis of 9-hydroxy-9-fluorenecarboxylic acid in hexafluoro-2-propanol (HFIP) generates a transient with max at 495 nm that reacts with nucleophiles such as methanol and bromide and is insensitive to oxygen. In the presence of 0.15 M trifluoroacetic acid, a different transient with max at 560 nm that also reacts with nucle...
Article
Abstract: In this work the pKas of six alkyl- and arylamine radical cations in aqueous solution have been determined by means of laser flash photolysis. The corresponding N-nitrosamines were used as precursors for the aminyl radicals which, upon protonation, formed the amine radical cations. The following pKas were obtained: 3.6 ? 0.2, 7.6 ? 0.3, 6...
Article
Absolute rate constants for (CF3)3C• addition to terminal olefins increase by roughly a factor of 30 for every 1 eV decrease in the ionization potential (IP) of the alkene. A similar decrease in IP increases the rate of addition of CF3• and n-C3F7• by a factor of only 3 or 4. The perfluoro-tert-butyl radical is, therefore, the most electrophilic, n...
Article
Rate constants for hydrogen atom abstraction from two water-soluble α-tocopherol (α-TOH, vitamin E) analogues by tert-butoxyl radicals have been measured at room temperature in four solvents, including water. The results imply that H-atom abstraction from α-TOH is 3.9 times slower in water than in benzene and yield a “reliable” Kamlet−Taft β solven...
Article
Laser flash photolysis has been used to determine the absolute rate constants for addition of several partially fluorinated n-alkyl radicals to three styrenes at 25 °C in Freon 113. Fluorination at the γ-position (RCF2CH2CH2•) gives radicals with essentially the same reactivity as non-fluorinated n-alkyls. The RCH2CF2CH2• and RCH2CH2CHF• radicals a...
Article
Absolute rate constants for hydrogen atom abstraction by alkoxyl radicals from phenol, aniline, and diphenylamine have been measured in 14 solvents at room temperature by laser flash photolysis. For all three substrates the rate constants decline as the solvent becomes a stronger hydrogen-bond acceptor (HBA). Thus, on changing the solvent from CCl4...
Article
Photolysis of N-nitrosamines in acidic acetonitrile produces aminium radical cations via protonation of the initially-formed aminyl radicals. The kinetics of these species can be monitored by transient UV spectroscopy via their absorption band which is found at ca. 300 nm in the case of the piperidinium radical, for example. By measuring the aminiu...
Article
Rate constants have been measured at 25 degrees C in 13 solvents (S) for abstraction of the phenolic hydrogen atom from alpha-tocopherol (TOH) by tert-butoxyl (BO.), k(TOH/BO)(S), and by 2,2-diphenyl-1-picrylhydrazyl (DPPH.), k(TOH/DO)(S), and in eight solvents for abstraction of the phenolic hydrogen atom from phenol by cumyloxyl, k(PhOH/CumO)(S),...
Article
The visible and UV absorptions of a variety of alkoxyl radicals have been examined by experiment and theory. In most solvents, the tert-butoxyl radical shows only a weak ''tail-end'' absorption in the UV region of the spectrum and no absorption in the visible region. However, a visible absorption band has been observed (lambda(max) = 440 nm) in the...
Article
The reactivity of the azidyl radical (N-3(.)) With olefins has been studied in acetonitrile solution using time-resolved UV-vis and infrared (TRIR) laser flash photolysis techniques. Azidyl radicals, formed by electron transfer from azide to excited state ketones, combine with excess azide in acetonitrile in an equilibrium reaction to form the pseu...
Article
Azide (N-3(-)) reacts with the triplet excited states of acetophenone (AP) benzophenone (BP) and benzil (Bz) by electron transfer in acetonitrile, generating the corresponding radical anion of the ketone and the azidyl radical (N-3(.)) UV-visible and time-resolved infrared (TRIR) nanosecond laser flash photolysis techniques have shown that the azid...
Article
Azide (N-3(-)) reacts with the triplet excited states of acetophenone (AP) benzophenone (BP) and benzil (Bz) by electron transfer in acetonitrile, generating the corresponding radical anion of the ketone and the azidyl radical (N-3(.)) UV-visible and time-resolved infrared (TRIR) nanosecond laser flash photolysis techniques have shown that the azid...
Article
Rate constants have been measured in nonaqueous media for hydrogen atom abstraction by the phenoxyl radical from some biologically important phenols and related compounds. Although the thermochemistry for these reactions must be very similar to the thermochemistry for H atom abstraction from the same substrate by a peroxyl radical, the phenoxyl rat...
Article
The 5-endo cyclization of the 2-formylbenzoyl radical (reaction 2) is shown to be a highly favored process relative to the alternative, 4-exo-trig ring closure. This evidence comes from product studies, including ESR and laser flash photolysis studies of transient radical intermediates, from a nitroxide trapping measurement of the rate constant for...
Article
Acetyl hypoiodite and a number of alkyl hypoiodites have been characterized as intermediates in the conversion of alcohols into alkoxyl radicals under Suárez (photostimulated iodosobenzenediactetate/iodine reagent) and Beebe (photolysed acetyl hypoiodite/alcohol) conditions.
Article
Absolute rate constants have been measured at 298 +/- 2 K for some reactions Of C2F5., n-C3F7., n-C7F15., and n-C8F17. by time-resolved (laser flash photolysis) and competition kinetics. The last three of these radicals exhibit essentially equal reactivities, but C2F5. is somewhat more reactive. The strongly electrophilic nature of these radicals i...
Article
The rate constant for the title reaction, k1, is 3.8 X 10(9) M-1 s-1 in water at 298 K and is greater-than-or-equal-to 10(8) M-1 s-1 in the gas phase at 603 K. It is concluded that two reports8,11 that this reaction is very slow in the gas phase, k1 less-than-or-equal-to 1.2 X 10(4) and approximately 2.3 X 10(6) M-1 s-1, are in error.
Article
Rate parameters are reported for hydrogen and deuterium abstraction of methyl radicals embedded in glassy mixtures of CH3OH and CD3OD. The mole fraction of CH3OH in these isotopomeric mixtures is 0, 0.05, 0.075, 0.10, 0.15, or 1. The nonexponential time dependence of the radical concentration is analyzed in terms of distributions of first-order rat...
Article
Cyclization of the 6,6-diphenyl-5-hexenyl radical (1) to the diphenylcyclopentylcarbinyl radical (2) was studied by indirect and direct methods. Indirect kinetic studies were accomplished by the PTOC-thiol method using hydrogen atom transfer trapping from thiophenol and from tert-butylthiol as the competing basis reactions over the temperature rang...
Article
The kinetics of the azobis(isobutyronitrile) initiated autoxidation of 1- and 2-methylnaphthalene have been studied from 30 to 60-degrees-C in the presence of sufficient tert-butyl hydroperoxide (1.0 M) to ensure that the tert-butylperoxyl radical totally dominates chain propagation and bimolecular peroxyl/peroxyl chain termination. Initial rate me...
Article
The rate of the self-initiated autoxidation of hexadecane at 160-degrees-C under 760 Torr of O2 is reduced by the addition of submolar concentrations of naphthalene or alkylnaphthalene. The kinetics of these (alkyl)naphthalene-modulated, self-initiated hexadecane autoxidations have been examined by monitoring hydroperoxide concentrations. Under sim...
Article
The photochemistry of spirooxazines I and II was examined using laser flash photolysis techniques. Both compounds lead to the formation of a strongly absorbing and long-lived, ring-opened photomerocyanine (PMC). In non-polar solvents the PMCs undergo photo-isomerization induced by visible light irradiation which ultimately regenerates the starting...
Article
Free-radical-chain reduction of organic halides is accomplished with heptamethyltrisilanethiol, a reducing agent combining the good hydrogen donating ability of a thiol and the excellent halogen abstracting properties of a silyl radical.
Article
Rate constants have been determined at 37°C for the ring opening of a variety of alkyl-substituted cyclopropylcarbinyl radical "clocks" by nitroxide radical trapping (NRT) using TEMPO. Relative yields of unrearranged and rearranged trialkylhydroxylamines were measured at various TEMPO concentrations, and these data were then combined with absolute...
Article
UV-visible absorption spectra and kinetic data obtained at room temperature are reported for three (alkenylcarbonyl)oxyls: trans-(CH3)3CCH = CHC(O)O., 1a; trans-C6H5CH = CHC(O)O., 1b; (CH3)2C = CHC(O)O., 1c; and two (alkynylcarbonyl)oxyls: (CH3)3CC = CC(O)O., 2a; C6H5C = CC(O)O., 2b. Rate constants for decarboxylation of 1a, 1b, 2a, and 2b are esti...
Article
Two sulfonyloxyl radicals, CH3S(=O)2O•, 2a, and 3-CF3C6H4S(=O)2O•, 2b, have been generated by 308-nm laser flash photolysis (LFP) of their parent symmetrical peroxides in CH3CN solution, in which they have lifetimes of 7-20 μs. Both radicals exhibit a broad, structureless absorption similar to that known for SO4•- with λmax ∼ 450 nm. This absorptio...
Article
Full-text available
Kinetic absorption spectroscopy, EPR, and tributyistannane product data indicate that the α-cyclopropylbenzyl radical (1a) undergoes reversible ring-opening to the 4-phenylbut-3-enyl radical (2a) and that equilibrium favours the ring-closed form, (1a).
Article
Dynamic EPR spectroscopy has been used to investigate the inversion of 1,3-dioxolan-2-yl and [2-D]-1,3-dioxolan-2-yl radicals. The former shows no detectable line broadening down to 93 K, which implies "instant" inversion on the EPR time scale, but the latter shows a temperature-dependent EPR spectrum from which the inversion rate constants have be...
Article
The photochemistry of the photomerocyanine from the title compound shows dramatic differences between polar and non-polar media; in the latter it involves the intermediacy of a ground state species with a lifetime of ca. 4µs which regenerates the merocyanine almost quantitatively.
Article
Laser flash photolysis (LFP) at wavelengths within the charge-transfer absorption present in CClâ solutions of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) yields the oxoammonium chloride of TEMPO, 1 (λ{sub max} = 460 nm), and the trichloromethyl radical in an essentially instantaneous (â¤18 ps) process. The primary photochemical event is an elect...
Article
The nitroxide radical, Tempo, has been shown to combine with alkyl radicals to form hydroxylamines with a rate constant of ca. 109 M-1 s-1 at room temperature and this reaction has been used to measure the rate of some very fast alkyl radical rearrangements. These calibrated “clock” reactions have then been used to investigate the “hydroxyl rebound...
Article
The title radical, Ph 2P(O)O •, has been generated by laser flash photolysis (LPP) of the peroxide [Ph 2P(O)O] 2 (1) in CH 3CN solution. It has a broad, structureless absorption extending from 400 to beyond 800 mn. Absolute bimolecular rate constants k for its reactions with various organic substrates have been measured by LFP. It has been found th...

Citations

... 6) using described procedures. [124][125][126][127] Then we carried out the typical iodination of aniline with the acetyl hypoiodite obtained in two conditions, first one without external addition of ammonium acetate, and the second using one equivalent of it. We obtained 51 % in first case and 73 % in second reaction. ...
... To date, there are only a few examples of amino acid derivatives of ferrocenecarboxylic acid in which ordered structural elements that could cause optical activity in the apsorption region of the ferrocene chromophore have been detected. Kraatz and co-workers [102] found a -turn structure in the crystalline state of ferrocenecarboxylic acid substituted with a tripeptide chain (-L-Pro-L-Pro-L-Phe-COOBzl), but did not study its conformation in solution in detail nor did they record its CD spectrum. By introducing a heterochiral peptide chain into the ferrocenecarboxylic acid, Hirao [103] prepared the enantiomeric derivatives Fn-CO-L-Ala-D-Pro-NH-4-Py and Fn-CO-D-Ala-L-Pro-NH-4-Py, which favour a -turnlike structure with the opposite sense of handedness, both in solution and in the solid state. ...
... Simple cyclopropylcarbinyl radicals (type A, Scheme 6a) ring-open very rapidly to form butenyl radicals. 14,15 The rate of the reverse reaction is comparatively very slow, so that these reactions routinely afford ring-opened products as the sole products from reactions. However, when the initial radical carbon is benzylic (type B) 14,15 or is a vinyl radical (type C), 16 then the cyclopropyl ring-opening is readily reversible and cyclic and/or open-chain products can result. ...
... They also found that the MC→SO transition occurs more efficiently in polar solvents, and the excitation of the SO form is the S 0 →S 1 transition which is consistent with the considerations of Schneider et al. Bohne et al. found [19] that in nonpolar media, the X form is in the ground state for a long time (~ 4 μs), after which it almost completely transforms into the MC form. In polar media, the X form in the ground state very fast transforms into the SO form. ...
... Carbenes are active transient intermediates in synthetic organic chemistry and their singlets are capable of abstracting heteroatoms from the heterocycles. [27] The alkyl-substituted carbene abstractions are much more favourable than those of the donor-substituted carbenes. [28] Unsaturated carbenes can cleave aziridines to give corresponding alkenes, since three membered ring systems at their ease form olefins through ring opening. ...
... Shaik et al., 2002). The carbon-centered radical is very short-lived and is rapidly hydroxylated and released from the active site as a metabolite much faster than the radical itself can escape from the hydrophobic enzyme active site (Heur et al., 1989;Bowry et al., 1990;Rota et al., 1997). This scenario reflects the metabolism of PCP by P450 2B6 and accounts for the partition ratio for P450 2B6 inactivation by PCP as being 45 (Jushchyshyn et al., 2003), which suggests that the majority of PCP secondary carbons are oxidized and released from the active site as hydroxylated metabolites (M1 and M2). ...
... Measured [I -] shows no change over time in any of the incubations investigated (Figures 4-6). This is also true for (Ingold et al., 1997;Konya et al., 2000;Heller and Croot, 2010) and ROS-induced oxidation products of CDOM have overlapping absorption peaks. Notably, the SOTS degradation products do not account for the same observations made for the same trend observed in H 2 O 2 observations. ...
... The high instability of alkyldiazonium salts is the main reason why the electrografting of alkyl groups on surfaces by reduction of alkyldiazonium salts has not been achieved until now [14]. Herein, we demonstrate the possibility of attaching alkyl groups on a copper surface by reduction of an acidic or basic aqueous nitrate solution in the presence of an alkylamine. ...
... 8 Although this process is thermally reversible in non-nucleophilic solvents and under inert atmosphere, bisketenes undergo irreversible reactions with H 2 O in usual biological media, thereby preventing ring closure to recover the initial squaramide motif. 9 This photobehavior prompted us to design a new class of squaramido-type ligands for new Pt(II) photocages. These new ligands may stabilize the Pt(II) center, preventing or substantially reducing its activity. ...
... [26][27][28][29][30] Although effective in the formation of α-X (X = O, N, S) divalent carbon species, 1,3,4-oxadiazolines were only evidenced to give alkylidene carbenes trapped as pyridinium ylides under laser flash photolysis (LFP) at 308 nm. [31][32][33] When exposed to UV light, non-stabilized diazo compounds are however generated. [34][35][36] While the first photolysis report dates back to 1968, 34 it was only recently that the Ley group proposed their application as diazo precursors in UV light-induced aryl-alkyl cross-coupling 37 and C-H functionalization reactions of aldehydes. ...