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Asymmetric organocatalysis is now recognized as the third pillar of asymmetric synthesis. Recent years have witnessed increasing interest towards the use of highly active and stereoselective organocatalysts. This critical review documents the advances in the development of chiral organocatalysts which are systematically used in ≤3 mol% loading in all the sub-areas of the field, namely aminocatalysis, Brønsted acids and bases, Lewis acids and bases, hydrogen bond-mediated catalysis, phase transfer and N-heterocyclic carbene catalyses (194 references).

In the last eight years, L-proline and L-proline derivatives, such as substituted prolinamides or pyrrolidines, have been successfully used as organocatalysts in several reactions. In this critical review we summarize the immobilization procedures of such organocatalysts highlighting their application, recoverability and reusability (86 references).

Molecular-wire behavior, that is, an exceptionally small attenuation factor (beta) of 0.01 +/- 0.005 A-1, has been established in novel C60-based donor-acceptor ensembles covalently connected through a series of fully conjugated phenylenevinylene oligomers of precise length and constitution.

A novel fullerene derivative, 1,1‐bis(4,4′‐dodecyloxyphenyl)‐(5,6) C61, diphenylmethanofullerene (DPM‐12), has been investigated as a possible electron acceptor in photovoltaic devices, in combination with two different conjugated polymers poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐para‐phenylene vinylene] (OC1C10‐PPV) and poly[3‐hexyl thiophene‐2,5‐diyl] (P3HT). High open‐circuit voltages, VOC = 0.92 and 0.65 V, have been measured for OC1C10‐PPV:DPM‐12‐ and P3HT:DPM‐12‐based devices, respectively. In both cases, VOC is 100 mV above the values measured on devices using another routinely used fullerene acceptor, [6,6]‐phenyl‐C61 butyric acid methyl ester (PCBM). This is somewhat unexpected when taking into account the identical redox potentials of both acceptor materials at room temperature. The temperature‐dependent VOC reveals, however, the same effective bandgap (HOMOPolymer–LUMOFullerene; HOMO = highest occupied molecular orbital, LUMO = lowest unoccupied molecular orbital) of 1.15 and 0.9 eV for OC1C10‐PPV and P3HT, respectively, independent of the acceptor used. The higher VOC at room temperature is explained by different ideality factors in the dark‐diode characteristics. Under white‐light illumination (80 mW cm–2), photocurrent densities of 1.3 and 4.7 mA cm–2 have been obtained in the OC1C10‐PPV:DPM‐12‐ and P3HT:DPM‐12‐based devices, respectively. Temperature‐dependent current density versus voltage characteristics reveal a thermally activated (shallow trap recombination limited) photocurrent in the case of OC1C10‐PPV:DPM‐12, and a nearly temperature‐independent current density in P3HT:DPM‐12. The latter clearly indicates that charge carriers traverse the active layer without significant recombination, which is due to the higher hole‐mobility–lifetime product in P3HT. At the same time, the field‐effect electron mobility in pure DPM‐12 has been found to be μe = 2 × 10–4 cm2 V–1 s–1, that is, forty‐times lower than the one measured in PCBM (μe = 8 × 10–3 cm2 V–1 s–1).

In this review, recent advances in asymmetric organocatalytic reactions carried out with variable amounts of water, from substoichiometric to a large excess (reaction medium), are discussed. We also summarize several proposed mechanisms for the different possibilities of the action of water both in the increased activity of the catalyst and in the asymmetric induction. Finally, the application of this catalytic methodology to the enantioselective synthesis of valuable compounds through enamine or iminium catalysis is presented.

In this perspective article the “release and catch” catalytic system concept is discussed. A “release and\ud catch” catalytic system is prepared by non-covalent immobilization of the catalytic moiety on a suitable support, but differently from the usual non-covalently supported catalyst, the catalytic moiety is released in solution over the course of the reaction and it is recaptured at the end of the reaction. Such a “catalyst-\ud sponge like” or “boomerang” system allows one to combine the benefits of homogeneous and heterogeneous catalysis and can be applied to organometallic-based catalysts, organocatalysts and metal-based catalysts

In this review, the most recent advances in the synthesis and catalytic applications of covalently supported ionic liquid (IL) phases will be discussed. This class of recyclable catalytic materials is based on the covalent attachment of several types of ammonium salts, usually imidazolium, but also thiazolium, triazolium, and pyrrolidinium salts, on the surface of different supports, for example, silica, periodic mesoporous organosilica, polystyrene, magnetic‐based materials, carbon nanotubes (NTs), halloysite NTs, polyhedral oligomeric silsesquioxane (POSS), and fullerenes. Moreover, poly(ionic liquid) materials, in which the IL‐based structure also acts as a support, will be considered. The synthetic applications of these materials will be presented, with special emphasis on their roles as catalysts, without added organocatalysts or metal‐based catalysts, as supports for organocatalysts, and as supports for metal‐based catalysts.