Control of the evolution of iron peroxide intermediate in superoxide reductase from Desulfoarculus baarsii. Involvement of lysine 48 in protonation

Superoxide reductase is a nonheme iron metalloenzyme that detoxifies superoxide anion radicals O(2)(?-) in some microorganisms. Its catalytic mechanism was previously proposed to involve a single ferric iron (hydro)peroxo intermediate, which is protonated to form the reaction product H(2)O(2). Here, we show by pulse radiolysis that the mutation of the well-conserved lysine 48 into isoleucine in the SOR from Desulfoarculus baarsii dramatically affects its reaction with O(2)(?-). Although the first reaction intermediate and its decay are not affected by the mutation, H(2)O(2) is no longer the reaction product. In addition, in contrast to the wild-type SOR, the lysine mutant catalyzes a two-electron oxidation of an olefin into epoxide in the presence of H(2)O(2), suggesting the formation of iron-oxo intermediate species in this mutant. In agreement with the recent X-ray structures of the peroxide intermediates trapped in a SOR crystal, these data support the involvement of lysine 48 in the specific protonation of the proximal oxygen of the peroxide intermediate to generate H(2)O(2), thus avoiding formation of iron-oxo species, as is observed in cytochrome P450. In addition, we proposed that the first reaction intermediate observed by pulse radiolysis is a ferrous-iron superoxo species, in agreement with TD-DFT calculations of the absorption spectrum of this intermediate. A new reaction scheme for the catalytical mechanism of SOR with O(2)(?-) is presented in which ferrous iron-superoxo and ferric hydroperoxide species are reaction intermediates, and the lysine 48 plays a key role in the control of the evolution of iron peroxide intermediate to form H(2)O(2).     

Iron-Catalyzed Halogen Exchange of Trifluoromethyl Arenes**

The facile production of ArCF₂X and ArCX₃ from ArCF₃ using catalytic iron(III)halides is reported, which constitutes the first iron-catalyzed halogen exchange for non-aromatic C−F bonds. Theoretical calculations suggest direct activation of C−F bonds by iron coordination. ArCX₃ and ArCF₂X products of the reaction are synthetically valuable due to their diversification potential. In particular, chloro- and bromodifluoromethyl arenes (ArCF₂Cl, ArCF₂Br respectively) provide access to a myriad of difluoromethyl arene derivatives (ArCF₂R). To optimize for mono-halogen exchange, a statistical method called Design of Experiments was used. Optimized parameters were successfully applied to electron rich and electron deficient aromatic substrates, and to the late stage diversification of flufenoxuron, a commercial insecticide. These methods are highly practical, being run at convenient temperatures and using inexpensive common reagents.     

Mechanistic diversity covering 15 orders of magnitude in rates: cyanide exchange on [M(CN)(4)](2-) (M = Ni, Pd, and Pt)

Kinetic studies of cyanide exchange on [M(CN)(4)](2-) square-planar complexes (M = Pt, Pd, and Ni) were performed as a function of pH by (13)C NMR. The [Pt(CN)(4)](2-) complex has a purely second-order rate law, with CN(-) as acting as the nucleophile, with the following kinetic parameters: (k(2)(Pt,CN))(298) = 11 +/- 1 s(-1) mol(-1) kg, DeltaH(2) (Pt,CN) = 25.1 +/- 1 kJ mol(-1), DeltaS(2) (Pt,CN) = -142 +/- 4 J mol(-1) K(-1), and DeltaV(2) (Pt,CN) = -27 +/- 2 cm(3) mol(-1). The Pd(II) metal center has the same behavior down to pH 6. The kinetic parameters are as follows: (k(2)(Pd,CN))(298) = 82 +/- 2 s(-1) mol(-1) kg, DeltaH(2) (Pd,CN) = 23.5 +/- 1 kJ mol(-1), DeltaS(2) (Pd,CN) = -129 +/- 5 J mol(-1) K(-1), and DeltaV(2) (Pd,CN) = -22 +/- 2 cm(3) mol(-1). At low pH, the tetracyanopalladate is protonated (pK(a)(Pd(4,H)) = 3.0 +/- 0.3) to form [Pd(CN)(3)HCN](-). The rate law of the cyanide exchange on the protonated complex is also purely second order, with (k(2)(PdH,CN))(298) = (4.5 +/- 1.3) x 10(3) s(-1) mol(-1) kg. [Ni(CN)(4)](2-) is involved in various equilibrium reactions, such as the formation of [Ni(CN)(5)](3-), [Ni(CN)(3)HCN](-), and [Ni(CN)(2)(HCN)(2)] complexes. Our (13)C NMR measurements have allowed us to determine that the rate constant leading to the formation of [Ni(CN)(5)](3-) is k(2)(Ni(4),CN) = (2.3 +/- 0.1) x 10(6) s(-1) mol(-1) kg when the following activation parameters are used: DeltaH(2)() (Ni,CN) = 21.6 +/- 1 kJ mol(-1), DeltaS(2) (Ni,CN) = -51 +/- 7 J mol(-1) K(-1), and DeltaV(2) (Ni,CN) = -19 +/- 2 cm(3) mol(-1). The rate constant of the back reaction is k(-2)(Ni(4),CN) = 14 x 10(6) s(-1). The rate law pertaining to [Ni(CN)(2)(HCN)(2)] was found to be second order at pH 3.8, and the value of the rate constant is (k(2)(Ni(4,2H),CN))(298) = (63 +/- 15) x10(6) s(-1) mol(-1) kg when DeltaH(2) (Ni(4,2H),CN) = 47.3 +/- 1 kJ mol(-1), DeltaS(2) (Ni(4,2H),CN) = 63 +/- 3 J mol(-1) K(-1), and DeltaV(2) (Ni(4,2H),CN) = - 6 +/- 1 cm(3) mol(-1). The cyanide-exchange rate constant on [M(CN)(4)](2-) for Pt, Pd, and Ni increases in a 1:7:200 000 ratio. This trend is modified at low pH, and the palladium becomes 400 times more reactive than the platinum because of the formation of [Pd(CN)(3)HCN](-). For all cyanide exchanges on tetracyano complexes (A mechanism) and on their protonated forms (I/I(a) mechanisms), we have always observed a pure second-order rate law: first order for the complex and first order for CN(-). The nucleophilic attack by HCN or solvation by H(2)O is at least nine or six orders of magnitude slower, respectively than is nucleophilic attack by CN(-) for Pt(II), Pd(II), and Ni(II), respectively.     

A Conductometric Sensor Specific for Cationic Surfactants

In this work, a fast, sensitive and miniaturised conductometric sensor based on interdigitated electrodes, working in differential mode, was developed for the determination of cationic surfactants. The membrane was composed of a polymer (PVC), a plasticizer (dinonylphtalate (DNP)) and a carrier (sodium tetraphenylborate (NaBΦ₄)). The sensor response was linear from at least 10^?9 M to 10^?2 M for dodecyltrimethylammonium (DTA⁺). No significant loss of sensor response was observed after 8 weeks. The sensor exhibited a lower sensitivity and a narrower dynamic range for tetrabutylammonium, decyltrimethylammonium and cetyltrimethylammonium cationic surfactants. A ten times lower sensitivity was observed for laurylsulfate anionic surfactant, (LS^?).     

Enantioselective straightforward access to benzo[b]thiophene analogs of Azatoxin

Horner-Wadsworth Emmons olefination followed by asymmetric hydrogenation allowed the first synthetic access to the chiral thiotryptophan with good enantiomeric excess. Oxazolidinone formation followed by a Pictet–Spengler condensation provided the benzothiophenic analog of Azatoxin.     

Solid State NMR and TG/MS Study on the Transformation of Methyl Groups During Pyrolysis of Preceramic Precursors to SiOC Glasses

The sol-gel method was used to prepare two different starting gels containing SiCH₃-groups for the preparation of SiOC ceramics. To understand the role of Si—H bonds in the incorporation of carbon into the SiOC network, gels prepared from a 1:2 mixture of triethoxysilane and methyldiethoxysilane (T^HD^H2) and solely methyltriethoxysilane (T^Me) were investigated. Thermogravimetric analysis coupled with mass spectroscopy (TG-MS) in inert atmosphere was performed to attain an insight into the decomposition reactions involved during gel-glass transformation. Samples calcined at different temperatures up to 1000°C were characterized by ²⁹Si and ¹³C magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy. The presence of SiH groups in the starting gel allows an efficient conversion of Si—CH₃ groups into CSi₄ sites at lower temperatures. As a result, despite a much lower amount of carbon in the starting T^HD^H2 gel (C/Si = 0.33) compared to the T^Me gel (C/Si = 1), the amount of carbon inserted into the SiOC network of both glasses is equivalent, but the T^Me sample contains the 10 fold amount of free carbon.     

Ferrocene incorporating host-guest dyads with electrochemically controlled three-pole hydrogen bonding properties

We describe the electrochemically controlled hydrogen bonding interactions between the isobutyl flavin/2,6-diferrocenylamidopyridine (2·5) and 9,10-phenanthrenequinone/1-ferrocenyl-3-hexylurea (4·6) dyads. Cyclic and square wave voltammetry studies have shown that the binding efficiencies between these moieties can be electrochemically actuated in non-polar (CH₂Cl₂ for 2·5) or polar (DMF for 4·6) organic solvents between three distinct states.     

Synthesis of sugar-based ethenyl ethers through a vinyl bis-sulfone methodology

The recently devised route to ethenyl ethers—i.e. 1,2-bis(phenylsulfonyl)ethylene (BPSE)-mediated conversion of alcohols into β-alkoxyvinyl sulfones followed by reductive desulfonylation—has been applied in the carbohydrate field to the synthesis of a number of vinyl-functionalised monosaccharides, a number of which had not been prepared via alternative routes.     

Hexacyanometalate molecular chemistry: di-, tri-, tetra-, hexa- and heptanuclear heterobimetallic complexes; control of nuclearity and structural anisotropy

Following a bottom-up approach to nanomaterials, we present a rational synthetic route to high-spin and anisotropic molecules based on hexacyanometalate [M(CN)(6)](3-) cores. Part 1 of this series was devoted to isotropic heptanuclear clusters; herein, we discuss the nuclearity and the structural anisotropy of nickel(II) derivatives. By changing either the stoichiometry, the nature of the terminal ligand, or the counterion, it is possible to tune the nuclearity of the polynuclear compounds and therefore to control the structural anisotropy. We present the synthesis and the characterisation by mass spectrometry, X-ray crystallography and magnetic susceptibility of bi-, tri-, tetra-, hexa- and heptanuclear species [M(CN)(n)(CN-M'L)(6-n)](m+) (with n=0-5; M=Cr(III), Co(III), M'=Ni(II); L=pentadentate ligand). Thus, with M=Cr(III), d(3), S=3/2, a dinuclear complex [Cr(III)(CN)(5)(CN-NiL(n))](9+), (L(n)=polydentate ligand) was built and characterised, showing a spin ground state, S(G)=5/2, with a ferromagnetic interaction J(Cr,Cu)=+18.5 cm(-1). With M=Co(III) (d(6), S=0) were built di-, tri-, tetra-, hexa and hepanuclear CoNi species: CoNi, CoNi(2), CoNi(3), CoNi(5) and CoNi(6). By a first approximation, they behave as one, two, three, five and six isolated nickel(II) complexes, respectively, but more accurate studies allow us to evaluate the weak antiferromagnetic coupling constant between two next-nearest neighbours M'-Co-M'.     

Enantioselective monoreduction of 2-alkyl-1,3-diketones mediated by chiral ruthenium catalysts. dynamic kinetic resolution

The reduction of 2-alkyl-1,3-diketones using (R,R)- or (S,S)-RuCl[N-(tosyl)-1,2-diphenylethylenediamine](p-cymene) in the presence of formic acid and triethylamine affords syn-2-alkyl-3-hydroxy ketones as the major products with high enantioselectivity. [reaction: see text]