Silvia Tabasso

The Heck Reaction Applied to 1,3- and 1,2-Unsaturated Derivatives, a Way towards Molecular Complexity

This review is an overview of the last ten years’ use of the Mizoroki–Heck coupling applied to 1,2- and 1,3-dienes. Since both these systems form π-allyl palladium intermediates in Pd(0) coupling, they show particular chemical behavior. Many examples of 1,2-dienes Heck reactions are presented. 1,2-Dienes are important substrates because of their high reactivity that makes them useful building blocks for the synthesis of biologically relevant structures.

Microwave-assisted flash conversion of non-edible polysaccharides and post-harvest tomato plant waste to levulinic acid

A microwave-assisted protocol for the conversion of non-edible polysaccharides and tomato plant waste to levulinic acid has been developed. Full conversion has been achieved in all cases at 2 min irradiation and clean levulinic acid was obtained without any purification in high yields (63–95%).

Structure–Function Relations of Strigolactone Analogs: Activity as Plant Hormones and Plant Interactions

Strigolactones (SLs) have several functions as signaling molecules in their interactions with symbiotic arbuscular mycorrhizal (AM) fungi and the parasitic weeds Orobanche and Striga. SLs are also a new class of plant hormone regulating plant development. In all three organisms, a specific and sensitive receptor-mediated perception system is suggested. By comparing the activity of synthetic SL analogs on Arabidopsis root-hair elongation, Orobanche aegyptiaca seed germination, and hyphal branching of the AM fungus Glomus intraradices, we found that each of the tested organisms differs in its response to the various examined synthetic SL analogs. Structure-function relations of the SL analogs suggest substitutions on the A-ring as the cause of this variation. Moreover, the description of competitive antagonistic analogs suggests that the A-ring of SL can affect not only affinity to the receptor, but also the molecules ability to activate it. The results support the conclusion that Arabidopsis, Orobanche, and AM fungi possess variations in receptor sensitivity to SL analogs, probably due to variation in SL receptors among the different species.

Microwave, ultrasound and ball mill procedures for bio-waste valorisation

Bio-waste valorisation has been one of the hottest research topics worldwide over the last decade. Following the biorefinery concept, the main goals have been the search for inexpensive renewable resources for the production of chemicals, materials and energy, the transformation of bio-waste into useful by-products and the development of new technologies for process intensification to make all these conversions economically profitable. Bio-waste is generally a negative-cost feedstock for the potential production of high value-added chemicals and bioenergy. The present review has the aim of describing existing studies and applications of non-conventional energy sources such as microwaves, ultrasound and ball milling within this field. We have focused our attention on suitable protocols for the conversion of biomass into fine chemicals. Comparisons with classic procedures are a good means with which to highlight the huge advantages and potential scalability of these so-called “enabling technologies”.

Benefits for agriculture and the environment from urban waste

Soluble bio-based substances (SBO) that have been isolated from urban biowaste have recently been reported to enhance plant leaf chlorophyll content and growth. The same SBO have also been shown to enhance the photochemical degradation of organic pollutants in industrial effluent. These findings suggest that SBO may promote either C fixation or mineralization, according to operating conditions. The present work aims to investigate SBO performance, as a function of source material. Thus, three materials have been sampled from a municipal waste treatment plant: (i) the digestate of the anaerobic fermentation of a humid organic fraction, (ii) a whole vegetable compost made from gardening residues and (iii) compost made from a mixture of digestate, gardening residues and sewage sludge. These materials were hydrolyzed at pH13 and 60°C to yield SBO that display different chemical compositions. These products were applied to soil at 30, 145 and 500 kg ha(-1) doses for tomato cultivation. Soil and plant leaf chemical composition, plant growth, leaf chlorophyll content and CO2 exchange rate as well as fruit quality and production rate were measured. Although it did not affect the soils chemical composition, SBO were found to significantly increase plant photosynthetic activity, growth and productivity up to the maximum value achieved at 145 kg ha(-1). The effects were analyzed as a function of SBO chemical composition and applied dose. The results of this work, compared with those of previous works, indicate that urban biowaste, if properly exploited, may furnish conjugate economic and environmental benefits, within a friendly sustainable ecosystem.

Strigolactone Analogs as Molecular Probes in Chasing the (SLs) Receptor/s: Design and Synthesis of Fluorescent Labeled Molecules

Originally identified as allelochemicals involved in plant-parasite interactions, more recently, Strigolactones (SLs) have been shown to play multiple key roles in the rhizosphere communication between plants and mycorrhizal fungi. Even more recent is the hormonal role ascribed to SLs which broadens the biological impact of these relatively simple molecules. In spite of the crucial and multifaceted biological role of SLs, there are no data on the receptor(s) which bind(s) such active molecules, neither in the producing plants nor in parasitic weeds or AM fungi. Information about the putative receptor of SLs can be gathered by means of structural, molecular, and genetic approaches. Our contribution on this topic is the design and synthesis of fluorescent labeled SL analogs to be used as probes for the detection in vivo of the receptor(s). Knowledge of the putative receptor structure will boost the research on analogs of the natural substrates as required for agricultural applications.

Enabling technologies built on a sonochemical platform: challenges and opportunities.

Scientific and technological progress now occurs at the interface between two or more scientific and technical disciplines while chemistry is intertwined with almost all scientific domains. Complementary and synergistic effects have been found in the overlay between sonochemistry and other enabling technologies such as mechanochemistry, microwave chemistry and flow-chemistry. Although their nature and effects are intrinsically different, these techniques share the ability to significantly activate most chemical processes and peculiar phenomena. These studies offer a comprehensive overview of sonochemistry, provide a better understanding of correlated phenomena (mechanochemical effects, hot spots, etc.), and pave the way for emerging applications which unite hybrid reactors.

LIC-KOR-promoted synthesis of alkoxydienyl amines: an entry to 2,3,4,5-tetrasubstituted pyrroles.

A stereoselective approach to the synthesis of (E)-alkoxydienylamines (2) is described, starting from alpha,beta-unsaturated acetals (1) and aryl imines, under superbasic conditions. These can be readily converted into alpha-arylglycine derivatives (3) by mild acidic hydrolysis or, in turn, cyclized under oxidative conditions in the presence of a Pd catalyst to 2,3,4,5-tetrasubstituted pyrroles (4).

Microwave-Assisted γ-Valerolactone Production for Biomass Lignin Extraction: A Cascade Protocol

The general need to slow the depletion of fossil resources and reduce carbon footprints has led to tremendous effort being invested in creating “greener” industrial processes and developing alternative means to produce fuels and synthesize platform chemicals. This work aims to design a microwave-assisted cascade process for a full biomass valorisation cycle. GVL (γ-valerolactone), a renewable green solvent, has been used in aqueous acidic solution to achieve complete biomass lignin extraction. After lignin precipitation, the levulinic acid (LA)-rich organic fraction was hydrogenated, which regenerated the starting solvent for further biomass delignification. This process does not requires a purification step because GVL plays the dual role of solvent and product, while the reagent (LA) is a product of biomass delignification. In summary, this bio-refinery approach to lignin extraction is a cascade protocol in which the solvent loss is integrated into the conversion cycle, leading to simplified methods for biomass valorisation.

Heck reaction on protected 3-alkyl-1,2-dien-1-ols: an approach to substituted 3-alkenylindoles, 2-alkoxy-3-alkylidene-2,3-dihydrobenzofuranes and -indolidines.

A phosphine-free annulation reaction has been exploited for the preparation of substituted 3-alkenylindoles, 2-alkoxy-3-alkylidene-2,3-dihydrobenzofuranes and -indolidines in good to excellent yields. This has been done by reaction of protected 3-alkyl-1,2-dienols with o-iodophenols or protected o-iodoanilines. Two different heterocyclic skeletons were obtained, depending on the electron-donating properties of the heteroatom involved in the annulation process.