Mechanistic and computational studies of oxidatively-induced aryl-CF3 bond-formation at Pd: rational design of room temperature aryl trifluoromethylation

This article describes the rational design of first generation systems for oxidatively induced Aryl-CF(3) bond-forming reductive elimination from Pd(II). Treatment of (dtbpy)Pd(II)(Aryl)(CF(3)) (dtbpy = di-tert-butylbipyridine) with NFTPT (N-fluoro-1,3,5-trimethylpyridinium triflate) afforded the isolable Pd(IV) intermediate (dtbpy)Pd(IV)(Aryl)(CF(3))(F)(OTf). Thermolysis of this complex at 80 °C resulted in Aryl-CF(3) bond-formation. Detailed experimental and computational mechanistic studies have been conducted to gain insights into the key reductive elimination step. Reductive elimination from this Pd(IV) species proceeds via pre-equilibrium dissociation of TfO(-) followed by Aryl-CF(3) coupling. DFT calculations reveal that the transition state for Aryl-CF(3) bond formation involves the CF(3) acting as an electrophile with the Aryl ligand serving as a nucleophilic coupling partner. These mechanistic considerations along with DFT calculations have facilitated the design of a second generation system utilizing the tmeda (N,N,N',N'-tetramethylethylenediamine) ligand in place of dtbpy. The tmeda complexes undergo oxidative trifluoromethylation at room temperature.     

Lowest energy electronic transition in aqueous Cl(-) salts: Cl(-) → (H2O)6 charge transfer transition

We use UV resonance Raman spectroscopy to probe the lowest energy allowed electronic transitions of aqueous solutions containing Cl(-) salts. We show that the waters hydrating the Cl(-) are involved in charge transfer transitions that transfer electron density from Cl(-) to the water molecules. These charge transfer transitions cause significant change in the H-O-H bond angle in the excited state, which results in a strong enhancement of the preresonance Raman intensity of the water bending modes. Our work gives the first insight into the lowest allowed electronic transition of hydrated Cl(-).     

Palladium-catalyzed 1,1-aryloxygenation of terminal olefins

This paper describes the 1,1-arylacetoxylation of diverse α-olefins using organostannanes and hypervalent iodine oxidants. The reaction provides a convergent approach for generating a C-C and a C-O bond as well as a new stereocenter in a single catalytic transformation.     

Silver-mediated trifluoromethylation of arenes using TMSCF3

The silver-mediated C-H trifluoromethylation of aromatic substrates using TMSCF(3) is described. The development, optimization, and scope of these transformations are reported. AgCF(3) intermediates are proposed.     

Prediction of oscillating thick cambered aerofoil aerodynamics by a locally analytic method

A complete first-order model and locally analytic solution method are developed to analyse the effects of mean flow incidence and aerofoil camber and thickness on the incompressible aerodynamics of an oscillating aerofoil. This method incorporates analytic solutions, with the discrete algebraic equations which represent the differential flow field equations obtained from analytic solutions in individual grid elements. The velocity potential is separated into steady and unsteady harmonic parts, with the unsteady potential further decomposed into circulatory and non-circulatory components. These velocity potentials are individually described by Laplace equations. The steady velocity potential is independent of the unsteady flow field. However, the unsteady flow is coupled to the steady flow field through the boundary conditions on the oscillating aerofoil. A body-fitted computational grid is then utilized. Solutions for both the steady and the coupled unsteady flow fields are obtained by a locally analytic numerical method in which locally analytic solutions in individual grid elements are determined. The complete flow field solution is obtained by assembling these locally analytic solutions. This model and solution method are shown to accurately predict the Theodorsen oscillating flat plate classical solution. Locally analytic solutions for a series of Joukowski aerofoils demonstrate the strong coupling between the aerofoil unsteady and steady flow fields, i.e. the strong dependence of the oscillating aerofoil aerodynamics on the steady flow effects of mean flow incidence angle and aerofoil camber and thickness.     

Synthesis of crescent aromatic oligoamides

[structures: see text] This article describes the synthetic procedures for the preparation of crescent (and helical) aromatic oligoamides developed in recent years in our laboratory. The large-scale preparation of a variety of monomers derived from various tetrasubstituted benzenes is presented. Three different strategies for constructing various oligomers consisting of meta- and meta/para-linked benzene residues are discussed. Factors affecting coupling efficiency and yields are analyzed. The developed synthetic methods have provided the basis for the preparation of longer oligomers and for the development of solid-phase synthesis.     

The Hardy classes for functions in the class MV[α, k]

Suppose that f(z) = z + a₂z² + ··· + a_nz_n + ··· is regular in the unit disc $\text{D}\text{with}\text{[f(z) f′}\text{(z)}\text{z] ≠ 0}\text{in}\text{D}$, and further let α ? 0 and k ? 2. If $\text{∝}{}^{\mathrm{2\pi }}{}_{\mathrm{o}}\text{¦}\text{Re}\text{{(1 ? α)z[}\text{f′(z)}\text{f(z)}\text{] + α(1 + z[}\text{f″(z)}\text{f′(z)}\text{])}¦ dθ ? kπ}\text{for}\text{z ? D}$, then f(z) is said to belong to the class MV[α, k]. This class contains many of the special classes of regular and univalent functions. The authors determine the Hardy classes of which f(z), f′(z) and f″(z) belong and obtain growth estimates of a_n.