Acyclic diastereoselection in prochiral radical addition to prochiral olefins

The stereochemical preference (syn or anti) when prochiral radicals add to prochiral acceptors is of fundamental interest. The primary focus of this research was to determine which factors influence the relative stereochemistry between the beta and gamma chiral centers when these are formed concurrently. While moderate diastereoselectivity was found for addition of alkyl (6a-d) and alpha-alkoxy radicals (16a-c) (< or =6:1 syn) to acceptors 4, 7, 8, 10, and 14, consistently high selectivity was observed with less reactive halogenated radicals (6f,g) (>15:1 anti). Steric influence in alkyl radical additions was difficult to evaluate due to decreased reactivity when using bulky reaction partners; however, more reactive alpha-alkoxy radicals, it was found that increasing steric bulk leads to moderate increases in selectivity. In addition, higher selectivity was observed when employing lanthanide Lewis acids whose environment (reactivity) was modified using achiral additives, suggesting a potentially simple means for selectivity enhancements in radical reactions. Overall these results indicate that significant stereoelectronic effects are necessary to achieve high levels of selectivity in prochiral radical additions to prochiral acceptors.     

Formal hydride transfer mechanism for photoreduction of 3-phenylquinoxalin-2-ones by amines. Association Of 3-phenylquinoxalin-2-one with aliphatic amines

The photophysical and photochemical behavior of 1-methyl-3-phenylquinoxalin-2-one (MeNQ) and 3-phenylquinoxalin-2-one (HNQ) in the presence of amines is reported. While HNQ fluorescence shows an auxochromic effect and a bathochromic shift with added amines, explained by association of HNQ with amine in the ground state and emission from both excited species HNQ and [HNQ-amine], both MeNQ and HNQ are photoreduced efficiently on irradiation in the presence of amines, leading to the semireduced quinoxalin-2-ones, MeNQH(-) and HNQH(-), respectively, via an electron-proton-electron transfer, with unit quantum yields at high amine concentrations. The semireduced quinoxalin-2-ones XNQH(-) (X = H, Me) revert almost quantitatively to the parent XNQ in a dark thermal reaction with an activation free energy for MeNQH(-) of 17.4 and 25.9 kcal/mol in acetonitrile and benzene, respectively. Kinetic and spectroscopic (UV and NMR) evidence supports the proposed reaction mechanism for the reversible photoreduction.     

Enantioselective addition of nitrones to activated cyclopropanes

In this paper, we demonstrate the first examples of chiral Lewis acid catalysis in the formation of tetrahydro-1,2-oxazines with very high enantioselectivity starting with diactivated cyclopropanes and nitrones (>90% yields and ee). Reactions with racemic substituted cyclopropanes provide approximately 1:1 diastereomeric tetrahydro-1,2-oxazine products with high enantioselectivity. Mechanistic information for the formation of the tetrahydro-1,2-oxazines is also detailed.     

ABSORPTION AND EMISSION STUDIES OF ELECTRONIC STATES OF N-ARYLBENZAMIDES

Abstract— Absorption and emission spectra of several N-arylbenzamides have been measured. The quantum yields for their fluorescence were found to be dependent on matrix viscosity and temperature. Singlet-triplet splittings for these compounds were determined from their emission spectra and found to be abnormally small for π. π* states (˜ 1500 cm^-1). Indeed, the phosphorescence maxima of N-arylbenzamides occur slightly to the blue relative to their fluorescence maxima. Intersystem crossing efficiencies were determined for several of these compounds and are consistent with S₁→ S ₀ radiationless decay.     

Electron spin resonance studies of 199HgH, 201HgH, 199HgD and 201HgD isolated in neon and argon matrices at 4K: an electronic structure investigation

Various isotopomers of the mercury hydride radical (HgH) have been generated in a microwave discharge and trapped in neon and argon matrices at 4 K for electron spin resonance (ESR) investigations. Both the dipolar (A_dip) and isotropic (A_iso) components of the nuclear hyperfine interactions have been directly measured for ¹⁹⁹Hg, ²⁰¹Hg, H and D. Electronic structure information for HgH in its X²Σ ground state obtained from the hyperfine data is compared with theoretical results from several different computational methods. The hyperfine interactions in HgH are unusually large with A_iso(¹⁹⁹Hg) = 6859(3), A_dip(¹⁹⁹Hg) = 446(3), A_iso(H) = 730(2) and A_dip(H) = 0(2) MHz. A standard analysis of the hyperfine interactions demonstrates the need for a more in-depth theoretical treatment of HgH that should include relativistic effects. An interesting shift in spin density is observed when deuterium replaces hydrogen in HgH. The decreased spin density on deuterium, which was demonstrated in earlier studies, can now be more fully investigated since these new measurements confirm an associated increase in spin density on mercury     

Improved models for the phase behaviour of hydrogen fluoride: chain and ring aggregates in the SAFT approach and the AEOS model

Hydrogen fluoride presents one of the strongest hydrogen bonds known. Ring aggregates exist both in the vapour and liquid phases at low temperatures resulting in an anomalously high low-temperature vapour pressure. The effect of ring-like aggregates on the vapour—liquid phase equilibria of associating fluids is studied within the framework of the statistical associating fluid theory (SAFT) and in the chemical model of Lencka and Anderko (AEOS). The SAFT approach incorporates separate contributions to describe chain formation, association (hydrogen bonding), and long range dispersion forces. The treatment of the association interactions stems from the thermodynamic perturbation theory of Wertheim. At the first level of approximation the contribution of ring-like aggregates is neglected and only chain- and treelike structures are treated. In this work an earlier extension of the approach to incorporate ring aggregates is used to model the phase behaviour of hydrogen fluoride. The chemical model of Lencka and Anderko for associating fluids is also considered together with a modification that takes into account the formation of ring aggregates. Vapour pressures and coexistence densities are examined together with heats of vapourization, and the calculations are compared with experimental data.