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Bibliografia
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Keywords
PHOTOCHEMISTRY, GREEN CHEMISTRY, ECO-COMPATIBLE SYNTHESIS, PHOTOCATALYSIS, HETEROGENEOUS CATALYSIS, OXIDATION, ALKYLATION, CATALYSTS, SUPPORTED TRANSTION METALS

Catalytic/photocatalytic oxidative activation in organic synthesis

Università degli Studi di Pavia
Abstract
The project aims to introduce new, more environment compatible, synthetic methods for fine chemicals, based on the mild and selective activation of strong chemical bonds by catalysis and photocatalysis with oxides and oxometallates, or new hybrid organic-inorganic materials. The reactions explored include 1) the photoinduced activation of the C-H bond in alkanes and simple aliphatic derivatives, both for the selective oxidation with molecular oxygen and for alkylation reactions; 2) the mild photochemical or thermal activation at the allylic or alpha-carboxy position in aliphatic derivatives and 3) mild oxygen insertion reactions (epoxidation, Baeyer-Villiger ester synthesis and sulfoxidation). New materials with catalytic and/or photocatalytic activity will be prepared by heterogeneization of titanium dioxide, of other oxides and of polyoxometallates on mesoporous materials, which are characterized by greater chemoselectivity and higher turn over number, avoiding leaching of metal ions and inactivation. Of the three collaborating units, one is mainly involved in the preparation of the new materials with (photo)catalytic activity and in developing thermal reactions, the other two in photocatalyzed oxygenation and respectively alkylation reactions, from both the preparative and mechanistic aspects. The actual significance of the methods will be pursued and assessed by using robust and reusable (photo)catalysts.

Principal Investigator
Angelo Albini Università degli Studi di PAVIA
Research Objectives
A major challenge to contemporary chemistry is developing new synthetic paths that are more environment friendly. ‘Green’ or sustainable chemistry has emerged as a discipline on its own, explicitly devoted to developing an environmental-conscious chemistry and over the past decade it has indeed demonstrated that new methodologies can be developed that protect human health and the environment. The most innovative aspect is devising new synthetic methods that start from non activated, easily available starting materials and lead through a short reactions sequence to functionalized derivatives under mild conditions, with high selectivity and minimal waste. This is a more and more difficult job with simple aliphatic derivatives that on the other hand are the cheapest and largely available feedstock. Internationally, the main approach involves the use of metal catalysts. Indeed, a large variety of transition metal complexes have been reported in recent years that operate with high selectivity and efficiency. However, these are often labile, expensive and toxic and at any rate much less used with aliphatic derivatives than with more active substrates. The present collaborative project follows a different path, involving photoinduced reactions and some particular catalytic reactions, based on (mesoporous) oxides, which are stable materials and are active either as catalysts or as photocatalysts (or both). Light is certainly a ‘green’ reagent and there is an extensive literature on >>>

Timescale
24 months
National and international background
As discussed in section, the basic intuition that generated this research project is that oxidative activation may be the way for discovering novel synthetic methods that can be applied to simple aliphatic derivatives, for which mild and selective procedures are less common. Furthermore, inorganic compounds and/or supported organic compounds may be convenient activators (i.e. more robust and/or easy to manage), either in the ground or in the excited state. Thus, an interdisciplinary effort for the study of catalytic or photocatalytic process was planned. The general target of the project is developing methods that are more environment-compatible in that shorter reaction sequences, milder conditions and less aggressive or polluting reagents are used. Obviously, the present project does not cover all of possible activations of aliphatic compounds, but rather centers on some classes of reactions that are considered exemplificative. The state of the art in the specific areas chosen is illustrated below.
A major part of this research plan involves photoinduced process. Light certainly is an innocuous reagent and allows obtaining deep-seated molecular transformations under mild conditions, as it has been demonstrated in a variety of synthetic procedures [1a]. In particular, light of the near UV and visible range (i.e. sunlight) is a completely renewable source of energy; its use requires milder conditions than thermal activated reactions; it may enable to carry out chemical >>>