Synthesis of 3,4-Dihydropyrano[c]chromenes Using Carbon Microsphere Supported Copper Nanoparticles (Cu-NP/C) Prepared from Loaded Cation Exchange Resin as a Catalyst.

AIM AND OBJECTIVE: The present study was performed with the aim to develop an efficient and environmentally benign protocol for the synthesis of biologically siginifcant 3, 4-dihydropyrano[c]chromenes using a new catalytic material. The protocol involves the use of a reusable, environment friendly materials and solvents with operational simplicity. MATERIALS AND METHODS: Carbon microsphere supported copper nanoparticles (Cu-NP/C) prepared from loaded cation exchange resin were synthesized, characterized with well versed analytical techniques such as XRD, SEM and Raman spectroscopy and the synthesized material was used as a catalyst for the environmentally benign synthesis of 3,4-dihydropyrano[c]chromenes. RESULTS: The formation of carbon microsphere supported copper nanoparticles (Cu-NP/C) prepared from loaded cation exchange resin was confirmed by XRD, SEM and Raman spectroscopy which was employed as a heterogeneous material for the synthesis of 3,4-dihydropyrano[c]chromenes. The products formed were characterized by the analysis of spectroscopic data - NMR, IR and mass. The safe catalytic system offers several advantages including operational simplicity, environmental friendliness, high yield, and reusability of catalyst and green chemical transformation. CONCLUSION: Herein we report an easy and efficient protocol for the one-pot synthesis of dihydropyrano[ c]chromenes using environmentally benign MCR approach in ethanol as the green solvent. The method developed herein constitutes a valuable addition to the existing methods for the synthesis of titled compounds.

Copper Acyl Salicylate Has Potential as an Anti-Cryptococcus Antifungal Agent.

The in vitro antifungal activity of aspirin against cryptococcal cells has been reported. However, the unwanted effects of aspirin may limit its clinical application. Conceivably, a derivative of aspirin could overcome this challenge. Toward this end, this study considered the usage of an aspirinate-metal complex, namely, copper acyl salicylate (CAS), as an anti-Cryptococcus antifungal agent. Additionally, the study examined the effects of this compound on macrophage function. The in vitro susceptibility results revealed that cryptococcal cells were vulnerable (in a dose-dependent manner) to CAS, which might have effected growth inhibition by damaging cryptococcal cell membranes. Interestingly, when CAS was used in combination with fluconazole or amphotericin B, synergism was observed. Furthermore, CAS did not negatively affect the growth or metabolic activity of macrophages; rather, it sensitized those immune cells to produce interferon gamma and interleukin 6, which, in turn, might have aided in the phagocytosis of cryptococcal cells. Compared to our aspirin data, CAS was noted to be more effective in killing cryptococcal cells (based on susceptibility results) and less toxic toward macrophages (based on growth inhibition results). Taking these findings together, it is reasonable to conclude that CAS may be a better anti-Cryptococcus drug that could deliver better therapeutic outcomes, compared to aspirin.

Concise and scalable synthesis of aspalathin, a powerful plasma sugar-lowering natural product.

Aspalathin (1), a dihydrochalcone C-glucoside, exhibits powerful plasma sugar-lowering properties and thus potentially could be used to treat diabetes. Small quantities occur in rooibos tea, manufactured via fermentation of the leaves of Aspalathus linearis, hence necessitating the need for an efficient and concise synthesis. Efforts to synthesize aspalathin (1) via coupling of a glucose donor to the nucleophilic phloroglucinol ring of the dihydrochalcone moiety have invariably failed, presumably because of ring deactivation by the electron-withdrawing carbonyl group. Reduction of the carbonyl group of a chalcone (15) and coupling of the resulting 1,3-diarylpropane (16) to tetra-O-benzyl-ß-D-glucopyranose afforded the C-glucosyl-1,3-diarylpropane (17). Regiospecific benzylic oxidation regenerated the carbonyl group and afforded the per-O-methylaspalathin (1a) quantitatively. This method was not successful with the per-O-benzyl-protected dihydrochalcone. However, the nucleophilicity of the phenolic hydroxy groups of the dihydrochalcone or its acetophenone precursor is not diminished by the carbonyl group. Thus, glucosylation of the di-O-benzylacetophenone (5c) at -40 °C afforded the α-O-glucoside (19) in 86% yield. Raising the temperature allowed facile BF3-catalyzed rearrangement to the ß-C-glucoside (6b), which upon hydrogenation, afforded aspalathin (1) in 80% overall yield [based on the usage of di-O-benzylphloroacetophenone (5c) and tetra-O-benzyl-1α-fluoro-ß-D-glucose (2e)].