This short review presents the current main chemical warfare agents and their most relevant simulants, and the recent catalytic and selective methods for their soft neutralization, potentially usable in the future as an alternative to “heavy” methods for decontamination.

The complexes between methyllithium and chiral 3-aminopyrrolidine (3-AP) lithium amides bearing a second asymmetric center on their lateral amino group were studied using multinuclear ((1)H, (6)Li, (13)C, (15)N) low-temperature NMR spectroscopies in tetrahydrofuran-d(8). The results indicate that lithium chelation forces the pyrrolidine ring of the 3-AP to adopt a norbornyl-like conformation and that robust 1:1 noncovalent complexes between methyllithium and 3-AP lithium amides form in the medium. A set of (1)H-(1)H and (1)H-(6)Li NMR cross-coupling correlations shows that the binding of methyllithium can take place along the "exo" or the "endo" face of this puckered structure, depending on the relative configuration of the lateral chiral group. This aggregation step renders the nitrogen of the 3-amino group chiral, the "exo" and "endo" topologies corresponding to the (S) and (R) configurations, respectively, of this atom. Density functional theory calculations show that the "exo" and "endo" arrangements are, for both diastereomers, almost isoenergetic even when solvent is taken into account. This result suggests that the formation of the mixed aggregates is under strict kinetic control. A relationship between the topology of these complexes and the sense of induction in the enantioselective alkylation of aromatic aldehydes by alkyllithiums is proposed.

The reproducible crystallisation of elusive polymorphs and solvates of molecular compounds at high pressure has been demonstrated through studies on maleic acid, malonamide, and paracetamol. These high-pressure methods can be scaled-up to produce bulk quantities of metastable forms that can be recovered to ambient pressure for subsequent seeding experiments. This has been demonstrated for paracetamol form II and paracetamol monohydrate. The studies also show that the particular solid form can be tuned by both pressure and concentration

The aim of this review is to present the latest developments in the stereoselective synthesis of conjugated dienes, covering the period 2005-2010. Since the use of this class of compounds is linked to the nature of their appendages (aryls, alkyls, electron-withdrawing, and heterosubstituted groups), the review has been categorized accordingly and illustrates the most representative strategies and mechanisms to access these targets.

A DFT analysis of the condensation of monomeric methyllithium and lithium dimethylamide (LMA), as well as their homo and hetero dimers, on formaldehyde and acetaldehyde is reported. A stable complex, exhibiting a directional interaction between a lone pair of the oxygen on the aldehyde and a lithium, is first found. At this stage, the aldehyde carbonyl and the Li-X (X = C or N) bonds lie in the same plane. To proceed, the condensation reaction has to go through a transition state that mainly consists of a rotation of the aldehyde plane, placing it perpendicular to the C-C or C-N forming bond. The reaction then leads, in a strongly exothermic final step, to the addition product that is a lithium alcoholate or alpha-amino alcoholate, associating into an hetero-aggregate with the remaining moiety of the initial dimer. From the relative heights of the activation barriers, it appears that, for the heterodimer MeLi-LMA, the formation of the C-N bond should be kinetically favored over the C-C one, while the lithium ethylate resulting from the C-C binding is the thermodynamic product. A decomposition of the activation energy barriers has been carried out in order to determine the physicochemical forces responsible for the variation of the condensation activation barriers with the structure of the final species formed. The results obtained are discussed in relation with corresponding experimental data.

The structure of the aggregates formed when mixing methyllithium and lithium chloride in THF has been studied by multinuclear magnetic resonance at 170 K. The data suggest that only one new entity is observed, that is the dimer [(MeLi)(LiCl)], in equilibrium (K approximately 0.6) with [MeLi](4) and [LiCl](2). NMR diffusion measurements lead to the conclusion that this dimer is trisolvated in THF at 170 K, a solvation scheme in agreement with DFT computations.

Nonempirical calculations on two copper cations (Cu(I)) interacting with a dioxygen molecule, taken as a model for the active site of oxyhemocyanin and oxytyrosinase, have been carried out to determine the most stable geometrical arrangement of this complex and its electronic structure. The results of closed-shell SCF computations show that the most stable electronic configuration of the complex is not the same for all distances between the oxygen molecule and the copper cations. Nevertheless, for the parallel as well as for the perpendicular arrangements of the two interacting entities, the lowest energy state of the complex is a singlet in agreement with EPR data. This result clearly shows that the magnetic characteristics of the active sites in question are due to a superexchange mechanism taking place through the sole dioxygen molecule. Moreover, the most stable conformation of the complexes obtained from this study for different Cu-Cu distances, corresponds to a location of the oxygen molecule between the two metal ions in agreement with the available experimental data on [(L"Cu)2-02]2+ model systems. Our results show also that this trans arrangement induces an important lengthening of the 0-0 bond. This feature, which is in agreement with Raman and X-ray data, is not found when the complex has the cis-g-dioxo conformation and provides further evidence for the validity of our simplified model. The electronic structure obtained for the most stable geometrical arrangement is discussed in relation to the experimenal spectroscopic data concerning model complexes as well as oxyhemocyanin and oxytyrosinase active sites themselves and with respect to possible mechanisms of action for the second of these enzymes.

The (1)J and (3)J(C-Li), (1)J(N-Li), and (2)J(Li-Li) NMR coupling constants have been calculated for various homogeneous and heterogeneous aggregates of methyllithium and lithium dimethylamide at the HF and MP2 levels of calculation. Ethereal solvation has also been taken into account either through a continuum model or through the explicit introduction of Me(2)O molecules. The results obtained are in good general agreement with the experimental data available for methyllithium itself or model alkyllithiums and supports the empirical rule proposed by Bauer, Winchester, and Schleyer to evaluate (1)J(C-Li) provided that calculations include solvent and/or aggregation effects.