Functionalization and Rearrangement of Spirocyclohexadienyl Oxindoles: Experimental and Theoretical Investigations

The preparation and functionalization of spirocyclohexa‐2,5‐diene oxindoles is described. The spirocyclic core of the title compounds was installed by using a SmI₂‐mediated cyclization of aryl iodobenzamides. Epoxidation with CF₃CO₃H was then carried out and was shown to occur with a high level of diastereocontrol: the reagent approaches the diene moiety syn to the amide group, which is likely to be as a consequence of hydrogen bonding between the amide C?O bond and the peracid hydrogen. Carbanionic functionalization of the spirocyclohexa‐2,5‐diene oxindoles was then examined, leading to an unprecedented rearrangement of the strained spiro system into dearomatized phenanthridinones. Upon treatment with lithium diisopropylamide (LDA) at ?40 °C, the dienes rearranged to provide a phenanthridinone lithium enolate intermediate that was trapped by electrophiles including alkyl halides and aldehydes. Interestingly, alkylation and hydroxyalkylation occurred with different regiocontrol. DFT calculations were performed that rationalize the observed skeleton rearrangement, emphasizing the role of LDA/diisopropylamine in this rearrangement. The proposed mechanism thus relies on a thermodynamically driven diisopropylamine‐mediated proton transfer with the cleavage of the diene–amide C?O bond as the key step.     

Estimating the intensity of a random measure by histogram type estimators

The purpose of this paper is to estimate the intensity of some random measure N on a set ${\mathcal{X}}$ by a piecewise constant function on a finite partition of ${\mathcal{X}}$ . Given a (possibly large) family ${\mathcal{M}}$ of candidate partitions, we build a piecewise constant estimator (histogram) on each of them and then use the data to select one estimator in the family. Choosing the square of a Hellinger-type distance as our loss function, we show that each estimator built on a given partition satisfies an analogue of the classical squared bias plus variance risk bound. Moreover, the selection procedure leads to a final estimator satisfying some oracle-type inequality, with, as usual, a possible loss corresponding to the complexity of the family ${\mathcal{M}}$ . When this complexity is not too high, the selected estimator has a risk bounded, up to a universal constant, by the smallest risk bound obtained for the estimators in the family. For suitable choices of the family of partitions, we deduce uniform risk bounds over various classes of intensities. Our approach applies to the estimation of the intensity of an inhomogenous Poisson process, among other counting processes, or the estimation of the mean of a random vector with nonnegative components.     

Dihydrogen to dihydride isomerization mechanism in [(C5Me5)FeH2(Ph2PCH2CH2PPh2)]+ through the experimental and theoretical analysis of kinetic isotope effects

The isomerization of complex [Cp*Fe(dppe)(eta2-H2)]+, generated in situ by low-temperature protonation of Cp*Fe(dppe)H with either HBF4 or CF3COOH, to the dihydride tautomer trans-[Cp*Fe(dppe)(H)2]+ is irreversible and follows first-order kinetics in the -10 to +15 degrees C range with Delta H double dagger = 21.6 +/- 0.8 kcal mol(-1) and DeltaS double dagger = 5 +/- 3 eu. The isomerization rate constant is essentially independent of the nature and quantity of a strong acid. Density functional theory (DFT) calculations on various models, including the complete system at both the quantum mechanics/molecular mechanics (QM/MM) and full QM levels, probe the relative importance of steric and electronic effects for the relative stability of the nonclassical and classical isomers and identify two likely isomerization mechanisms: a "direct" pathway involving simultaneous H-H bond breaking and cis-trans isomerization and a "via Cp" pathway involving agostic C5Me5H intermediates. Both pathways are characterized by activation energies in close correspondence with the experimental value (21.3 and 22.2 kcal mol(-1), respectively). Further kinetic studies were carried out for the Cp*Fe(dppe)H + CF3COOD and Cp*Fe(dppe)D + CF3COOD systems at 273 K. The [Cp*Fe(dppe)(eta2-HD)]+ complex establishes a very rapid isotope redistribution equilibrium with the eta2-H2 and eta2-D2 analogues. The equilibrium constant value (K = 3.3 +/- 0.3) indicates a significant equilibrium isotope effect. Simulation of the rate data provides access to the individual isomerization rate constants kHH, kHD, and kDD for the three isotopomers, yielding kinetic isotope effects: kHH/kHD = 1.24 +/- 0.01 and kHD/kDD = 1.58 +/- 0.01 (and, consequently, kHH/kDD = 1.96 +/- 0.02). The analysis of the DFT-calculated frequencies, using the [Cp*Fe(dhpe)H2]+ model system, for the [Cp*Fe(dhpe)(eta2-XY)]+ isotopomers as well as transition states for the "direct" (TSdir) and "via Cp" (TSrot) pathways (X = H, D) allowed the computation of the expected isotope effects. A comparison with the experiment strongly suggests that the mechanism occurs via the "direct" pathway for the present system, although the small difference in the calculated energy barriers suggests that the "via Cp" pathway may be preferred in other cases.     

High-accuracy extrapolated ab initio thermochemistry. II. Minor improvements to the protocol and a vital simplification

The recently developed high-accuracy extrapolated ab initio thermochemistry method for theoretical thermochemistry, which is intimately related to other high-precision protocols such as the Weizmann-3 and focal-point approaches, is revisited. Some minor improvements in theoretical rigor are introduced which do not lead to any significant additional computational overhead, but are shown to have a negligible overall effect on the accuracy. In addition, the method is extended to completely treat electron correlation effects up to pentuple excitations. The use of an approximate treatment of quadruple and pentuple excitations is suggested; the former as a pragmatic approximation for standard cases and the latter when extremely high accuracy is required. For a test suite of molecules that have rather precisely known enthalpies of formation {as taken from the active thermochemical tables of Ruscic and co-workers [Lecture Notes in Computer Science, edited by M. Parashar (Springer, Berlin, 2002), Vol. 2536, pp. 25-38; J. Phys. Chem. A 108, 9979 (2004)]}, the largest deviations between theory and experiment are 0.52, -0.70, and 0.51 kJ mol(-1) for the latter three methods, respectively. Some perspective is provided on this level of accuracy, and sources of remaining systematic deficiencies in the approaches are discussed.     

Stability of the gold/silica thin film interface: electrochemical and surface plasmon resonance studies

This article reports chemical stability studies of a gold film electrode coated with thin silicon oxide (SiOx) layers using electrochemical, surface plasmon resonance (SPR) and atomic force microscopy (AFM) techniques. Silica films with different thicknesses (d = 6.4, 9.7, 14.5, and 18.5 nm) were deposited using a plasma-enhanced chemical vapor deposition technique (PECVD). For SiOx films with d >/= 18.5 nm, the electrochemical behavior is characteristic of a highly efficient barrier for a redox probe. SiOx films with thicknesses between 9.5 and 14.5 nm were found to be less efficient barriers for electron transfer. The Au/SiOx interface with 6.4 nm of SiOx, however, showed an enhanced steady-state current compared to that of the other films. The stability of this interface in solutions of different pH was investigated. Whereas a strongly basic solution led to a continuous dissolution of the SiOx interface, acidic treatment produced a more reticulated SiOx film and improved electrochemical behavior. The electrochemical results were corroborated by SPR measurements in real time and AFM studies.     

C-H bond activation of arenes by a transient eta2-cyclopropene niobium complex

The intermolecular C-H bond activation of benzene occurs under very mild conditions (room temperature) via a rare stereospecific 1,3-H addition on an unsaturated eta2-cyclopropene intermediate generated by a beta-H abstraction of CH4 from TpMe2NbMe(c-C3H5)(MeCCMe) to give TpMe2NbPh(c-C3H5)(MeCCMe).     

Synthesis of fullerohelicates and fine tuning of the photoinduced processes by changing the number of addends on the fullerene subunits

Two fullerene-substituted m-phenylene-bis-phenanthroline ligands have been prepared. The synthesis of the first derivative (L1) is based on an esterification reaction between a C_s symmetrical cis-2 fullerene bis-adduct bearing a carboxylic acid function and a bis-phenanthroline alcohol (5). The second ligand (L2) has been obtained by reaction of a bis-phenanthroline malonate (9) and C₆₀ under Bingel conditions. The copper(I) complexes of L1 and L2 have been prepared by treatment with a slight excess of Cu(CH₃CN)₄BF₄. NMR spectroscopy and mass spectrometry analysis have unambiguously shown that these complexes are bis-copper(I) helicates substituted with two fullerene moieties. The photophysical properties of the copper(I) complexes Cu₂(L1)₂ and Cu₂(L2)₂ have been investigated. In both systems photoinduced electron transfer from the central metal-complexed unit to the external fullerenes may occur, in principle, by excitation of both moieties. However, this is found to be the case only for the methanofullerene system Cu₂(L2)₂. Unexpectedly, for Cu₂(L1)₂, photoexcitation of the peripheral carbon spheres is followed by regular internal deactivation. Possible reasons for this behavior are examined in light of current theories for photoinduced energy and electron transfer.     

Radical-mediated 5-exo-trig cyclizations of 3-silylhepta-1,6-dienes

Regioselectivity of the sulfonyl radical mediated 5-exo-trig cyclization of 3-silylheptadienyl systems 3a-d has been studied. At low temperature, the reaction of the sulfonyl radical occurs regioselectively at the allylsilane terminus, while a reversal of regioselectivity is observed at 80 degrees C. This general trend has been rationalized on the basis of polar effects and radical stabilization. Thiyl-mediated radical cyclization of dienes 3a, 3c-d, 7 with subsequent sulfur atom transfer was also studied, providing thiabicyclo[3.3.0] skeleton in one step with excellent stereocontrol.     

Shape distortions induced by convective effect on hot object in visible, near infrared and infrared bands

The goal of this study is to examine the perturbation induced by the convective effect (or mirage effect) on shape measurement and to give an estimation of the error induced. This work explores the mirage effect in different spectral bands and single wavelengths. A numerical approach is adopted and an original setup has been developed in order to investigate easily all the spectral bands of interest with the help of a CCD camera (Si, 0.35–1.1 μm), a near infrared camera (VisGaAs, 0.8–1.7 μm) or infrared cameras (8–12 μm). Displacements due to the perturbation for each spectral band are measured and finally some hints about how to correct them are given.     

Use of ram extruder as a combined rheo-tribometer to study the behaviour of high yield stress fluids at low strain rate

We propose in this work to provide an efficient and simple extruder device able to evaluate the rheological and tribological behaviour of high yield stress fluids, such as extrudible materials. An extruder able to measure simultaneously both the friction force acting on the extruder wall and the total extrusion force is developed. Based on previous studies, an efficient and accurate method of data analysis is then proposed and applied in order to obtain both a flow curve and a tribological law. Experimental tests are performed on soft modelling clay, kaolin paste and cement-based materials. Results are compared to conventional rheometry measurements. This comparison helps to evaluate the accuracy of the proposed experimental device and procedure.