Highly cross-linked imidazolium-based materials,obtained by radical oligomerization of bisvinylimidazolium\ud salts in the presence of 3-mercaptopropyl-modified silica gel, were used as supports for palladium catalysts. Thanks to the high imidazolium loading these materials were able to support a high amount of the metal (10 wt%). Such materials\ud were characterized by several techniques (13C magic angle spinning nuclear magnetic resonance, the Brunauer–\ud Emmett–Teller technique, X-ray photoelectron spectroscopy, and transmission electron microscopy).\ud The palladium catalysts displayed good activity allowing the synthesis of several biphenyl compounds\ud in high yields working with only 0.1 mol% of palladium loading at 50 8C in ethanol/water under batch condition. Moreover, a flow apparatus, to optimize\ud the efficiency of the isolation of the pure products and minimize waste (E-factor), was investigated.\ud For the first time the palladium catalyst and base(K2CO3) were placed in two separate columns allowing an easy recovery of the products with very low\ud E-factor values (<4). Waste production was reduced by over 99% compared to classic batch conditions.\ud Because of the high Pd loading only 42 mg of catalysts were employed in the Suzuki reaction between 160 mmol of 4-bromotoluene and 180 mmol of phenylboronic acid. No loss in activity was observed

γ-Valerolactone (GVL) can be a valid biobased replacement for toxic dipolar aprotic solvents especially in widely used cross-coupling reactions. In this contribution, we have proved that GVL can be a useful medium for the Hiyama reaction, and we developed a practical and efficient protocol for the Hiyama coupling using a nonexpensive and commercially available heterogeneous palladium catalyst without the use of any ligand or additive. Desired cross-coupling products 3a−m have been obtained in good to excellent yields (74−94%).

In this contribution we have used green metrics analysis to compare the material efficiency, environmental impact, and safety-hazard impact in order to compare flow and batch procedures for azidation of α,β-unsaturated carbonyls.

No abstract

Under solvent-free conditions the reaction of epoxides 1a–i with trimethylsilylazide (2) catalyzed by poly- stiryl-supported fluoride (PS-DABCOF2) has led to the efficient preparation of the corresponding O-TMS protected 1,2-azido alcohols 3a–i that, by treatment with Dowex-H, gave the related 1,2-azido alcohols 4a–i in excellent yields (83–99% and 82–96%, respectively). The use of a flow procedure has allowed us to significantly minimize waste in the preparation of representative 1,2-azido alcohols 4a, 4c and 4i that have been obtained with E-factors of 1.6, 2.1, and 1.9, respectively. The 1,2-amino alcohols 5a, 5c and 5f have been also prepared, in quantitative yields, by reduction of the corresponding O-TMS protected 1,2-azido alcohols 3a, 3c, and 3f by Pd on the Al3O3/HCOOH system

No abstract

Diels-Alder cycloaddition reactions of 3-cyanocoumarin, hydroxy-substituted 3-cyanocoumarins and mesyl-substituted 3-cyano-coumarins with methyl-1,3-butadienes carried out under high pressure (11 kbar) are reported. Activation by high pressure allows these reactions to proceed satisfactorily under mild conditions to produce 6a-cyano-hydroxy- and 6a-cyano-mesyl-tetrahydro-6H-benzo[c]chromen-6-ones in moderate to excellent yield. The synthesis of cis-1-hydroxy-9-methyl-3-pentyl-6a,7,10,10a-tetrahydro-benzo[c]chromen-6-one as precursor of Delta(6)-3,4-cis-cannabidiol (Delta(6)-cis-CBD) and Delta(8)-cis-tetrahydrocannabinol (Delta(8)-cis-THC) is outlined.

Biostimulants are receiving increasing attention for their beneficial effects on crops, driving interest in identifying new plant extracts that could exert such stimulatory effects. This work aimed to evaluate the potential of an aqueous extract obtained from duckweed (Lemna minor L.), a freshwater species, to act as a biostimulant in maize. For this purpose, duckweed plants were collected from a natural basin and then transferred, stabilized, and grown under controlled conditions. The duckweed extract was first characterized through untargeted profiling, which revealed an abundance of bioactive phytochemicals. A relatively high amount of low-molecular-weight secondary metabolites such as phenolics (6714.99 mg kg−1) and glucosinolates (4563.74 mg kg−1) were present in the plant extract. Maize seeds were primed with different concentrations of this extract (0.01%, 0.05%, 0.50%, and 1.00%, dry weight/water volume), and some physiological and biochemical traits of the crop were recorded. The duckweed extract improved maize germination, biomass, leaf area, pigment content, and vigor index. The most effective treatment was the 0.50% concentration, which improved the majority of the measured growth traits. The extract at concentrations of 0.05%, 0.50%, and 1.00% stimulated the assimilation of nitrogen (N), phosphorous (P), potassium (K), calcium (Ca), magnesium (Mg), sodium (Na), iron (Fe), and copper (Cu). In summary, this study revealed that duckweed is a promising species that can be cultured and grown under controlled conditions for obtaining extracts with biostimulant properties.