Frank Alber,†,‡,§ Gerd Folkers,‡ and Paolo Carloni*,†,§,| International School for AdVanced Studies SISSA/ISAS, Via Beirut 4 I-34014 Trieste, Italy, Department of Pharmaceutical Chemistry, Swiss Federal Institute of Technology (ETH), CH-8057 Zürich, Switzerland, INFM-Istituto Nazionale per la Fisica della Materia, Italy, International Centre for Genetic Engineering and Biotechnology, AREA Scien...

A plausible route for the spontaneous synthesis of an activated ribonucleotide that is poised for polymerization has been put forth (Powner et al. (2009) Nature, 459, 239-242). A key step in this route necessitates the regioselective phosphorylation of the secondary alcohol on C(3') of an anhydroarabinonucleoside in the presence of the primary alcohol on C(5'). Here, we propose that this regios...

It has recently been pointed out that current density functionals are inaccurate for computing stereoelectronic effects and energy differences of isomerization reactions and isodesmic reactions involving alkanes; this has been interpreted as an incorrect prediction of medium-range correlation energies. This letter shows that the recently published M05-2X functional has good accuracy for all thr...

The n-butyramido, isobutyramido, benzamido, and furancarboxamido functions profoundly modulate the electronics of the stilbene olefinic and NH groups and the corresponding radical cations in ways that influence the efficiency of the cyclization due presumably to conformational and stereoelectronic factors. For example, isobutyramido- stilbene undergoes FeCl(3) promoted cyclization to produce on...

We report a one-step synthesis of the phosphine, PPh(2)(i)C(3)F(7) from commercially available precursors. The stereoelectronic properties of the phosphine were probed by coordination to transition metals. Mo(CO)(5)PPh(2)(i)C(3)F(7) was synthesised and the synthesis and structure of trans-PtCl(2)(PPh(2)(i)C(3)F(7))(2) are described. PPh(2)(i)C(3)F(7) was found to be a bulky electron-withdrawing...

Stereoelectronic effects modulate molecular structure, reactivity, and conformation. We find that the interaction between the ester and carboxyl moieties of aspirin has a previously unappreciated quantum mechanical character that arises from the delocalization of an electron pair (n) of a donor group into the antibonding orbital (π*) of an acceptor group. This interaction affects the physicoche...

This study was aimed at determining the effect, if any, that steric factors may have on the diastereoselectivity in the spiroannulation of simple phenols. A series of phenols bearing different size substituents ortho to the phenolic hydroxyl were synthesized and spiroannulated to the corresponding spiroethers in good to excellent yields (76-94%). However, the diastereoselectivity of the reactio...

Eeny, meeny, miny ... enaminones! Lactams and imides have been shown to consistently provide enantioselectivities substantially higher than other substrate classes previously investigated in the palladium-catalyzed asymmetric decarboxylative allylic alkylation. Several new substrates have been designed to probe the contributions of electronic, steric, and stereoelectronic factors that distingui...