The term "organocatalysis" describes the acceleration of chemical reactions through the addition of a substoichiometric quantity of an organic compound. The interest in this field has increased spectacularly in the last few years as result of both the novelty of the concept and, more importantly, the fact that the efficiency and selectivity of many organocatalytic reactions meet the standards of established organic reactions. Organocatalytic reactions are becoming powerful tools in the construction of complex molecular skeletons. The diverse examples show that in recent years organocatalysis has developed within organic chemistry into its own subdiscipline, whose "Golden Age" has already dawned.

In the Golden Age of Organocatalysis

Small-molecule H-bond donors in asymmetric catalysis.

Asymmetric 1,3-Dipolar Cycloaddition Reactions

Huisgen's 1,3-dipolar cycloadditions become nonconcerted when copper(I) acetylides react with azides and nitrile oxides, providing ready access to 1,4-disubstituted 1,2,3-triazoles and 3,4-disubstituted isoxazoles, respectively. The process is highly reliable and exhibits an unusually wide scope with respect to both components. Computational studies revealed a stepwise mechanism involving unprecedented metallacycle intermediates, which appear to be common for a variety of dipoles.

Copper(I)-catalyzed synthesis of azoles. DFT study predicts unprecedented reactivity and intermediates.

Asymmetric multicomponent reactions involve the preparation of chiral compounds by the reaction of three or more reagents added simultaneously. This kind of addition and reaction has some advantages over classic divergent reaction strategies, such as lower costs, time, and energy, as well as environmentally friendlier aspects. All these advantages, together with the high level of stereoselectivity attained in some of these reactions, will force chemists in industry as in academia to adopt this new strategy of synthesis, or at least to consider it as a viable option. The positive aspects as well as the drawbacks of this strategy are discussed in this Review.

Asymmetric multicomponent reactions (amcrs): the new frontier

/pdf/on-the-crystal-structures-of-some-phases-in-the-al2o3-nb2o5-1h13md8oti.pdf

On the Crystal Structures of Some Phases in the Al2O3-Nb2O5-System.

A series of four-co-ordinate nickel(II) N2X2 complexes (X = NH, O or S) with tetradentate Schiff-base ligands incorporating pyrazole has been prepared in order to compare the influence on the nickel(II) centre of the donor atoms in N2(NH)2 and N2S2 complexes versus N2O2 complexes. In each case, two identical parts of the ligand are linked by a two- or three-carbon aliphatic chain (n = 2 or 3). Crystal structures have been determined for a n = 3 N2(NH)2 complex, for two n = 3 N2S2 complexes and for a n = 2 N2O2 complex. All of the complexes have been investigated in solution by spectroscopic methods (UV/VIS/NIR, 1H NMR). The n = 2 and 3 N2(NH)2 complexes and the n = 2 N2S2 complexes are fully diamagnetic. An extension of the chain linking the two halves of the ligand from two to three carbon atoms induces a spin-equilibrium process (S = 0 ⇄ S = 1) for the resulting N2S2 complex (ΔG = 19–26 kJ mol–1 at 50 °C). Ligand-field parameters have been derived from the electronic spectra and the electrochemical properties of the N2S2 complexes have been investigated by cyclic voltammetry. From these results it is clear that low-spin character is emphasized in N2(NH)2 and N2S2 complexes of nickel(II) when compared with the corresponding N2O2 complexes.

Nickel(II) N2X2 Schiff-base complexes incorporating pyrazole (X = NH, O or S): syntheses and characterization†

Synthesis and properties of novel cobalt(III) and nickel(II) complexes with coordinated azetidine nitrogens: crystal structure of mer-tris(3-(aminomethyl)-3-methylazetidine)cobalt(III) chloride

/pdf/the-crystal-structure-of-rubidium-triselenocyanate-2e1df6mxqc.pdf

The Crystal Structure of Rubidium Triselenocyanate Hemihydrate.

Etude de la reduction electrochimique du disulfure de carbone en presence de monosulfure de carbone. Structure cristalline du (bis-methylthiomethylene-2 dimethylthio-4,5) dithiole-1,3, forme par methylation du tetrathiooxalate

/pdf/the-role-of-carbon-monosulfide-in-the-electrochemical-2z1q577xp0.pdf

The role of carbon monosulfide in the electrochemical preparation of 4,5-bis(methylthio)-1,3-dithiole-2-thione

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