Asymmetric Total Synthesis of Rumphellclovane E.

The first asymmetric total synthesis of rumphellclovane E, a clovane-type sesquiterpenoid, has been accomplished in eight steps from commercially available (R)-carvone. Key elements of the synthesis include Rh-catalyzed cyclopropanation, iron-catalyzed intramolecular reductive aldol reaction, and SmI2-mediated chemo- and diastereoselective reduction of the cyclopentanone.

Influenza antiviral activity of F- and OH-containing isopulegol-derived octahydro-2H-chromenes.

We synthesized fluoro- and hydroxy-containing octahydro-2H-chromenes by the Prins reaction starting from a monoterpenoid (-)-isopulegol and a wide range of aromatic aldehydes in the presence of the BF3∙Et2O/H2O system acting as both an acid catalyst and a fluorine source. Activity of the produced compounds against the influenza A/Puerto Rico/8/34 (H1N1) virus was studied. The highest activity was demonstrated by fluoro- (11i) and hydroxy-containing (10i) derivatives of 2,4,6-trimethoxybenzaldehyde. The most pronounced virus-inhibiting effect of compounds 10i and 11i was observed at an early stage of infection. These compounds were supposed to be capable of binding to viral hemagglutinin, which is an agreement with data on the effect of compounds 10i and 11i on the viral fusogenic activity as well as by molecular docking studies.

Transformations of Monoterpenes with the p-Menthane Skeleton in the Enzymatic System of Bacteria, Fungi and Insects.

The main objective of this article was to present the possibilities of using the enzymatic system of microorganisms and insects to transform small molecules, such as monoterpenes. The most important advantage of this type of reaction is the possibility of obtaining derivatives that are not possible to obtain with standard methods of organic synthesis or are very expensive to obtain. The interest of industrial centers focuses mainly on obtaining particles of high optical purity, which have the desired biological properties. The cost of obtaining such a compound and the elimination of toxic or undesirable chemical waste is important. Enzymatic reactions based on enzymes alone or whole microorganisms enable obtaining products with a specific structure and purity in accordance with the rules of Green Chemistry.

Phosphonate functionalized carbon spheres as Brønsted acid catalysts for the valorization of bio-renewable α-pinene oxide to trans-carveol.

Herein, we report a simple route for the synthesis of phosphonate functionalized Brønsted solid acid carbon spheres as heterogeneous catalyst for the valorization of bio-derived α-pinene oxide. The Brønsted acidity was generated via two steps; hydrothermal carbonization of sugar to produce carbon microspheres followed by PCl3 treatment to form phosphonate functionalized carbon. The presence of phosphonate was confirmed by CP-MAS 31P and 13C NMR. In addition, the presence of the P-C, O-P-C and HO-P[double bond, length as m-dash]O bonds of the phosphonate group was confirmed by FT-IR, 31P NMR, and XPS. SEM-EDAX analysis revealed the presence of a phosphorus content of ∼1.71 wt% on the surface of the catalyst while elemental mapping showed a uniform dispersion of phosphorus over the carbon spheres. The as-synthesized Brønsted solid acid catalyst was used for the isomerization of α-pinene oxide which gave 100% conversion with 67% trans-carveol selectivity in highly polar basic solvent in 1 h reaction time. Also, the catalyst showed good recyclable activity even after five cycles.

Asymmetric synthesis of trans-p-menth-3-ene-1,2,8-triol, the monoterpene isolated from herbal plants.

The monoterpene, trans-p-menth-3-ene-1,2,8-triol, is a naturally occurring alcohol isolated from several herbal plants. In the present work, the asymmetric synthesis of both enantiomers of this natural product was achieved using Sharpless asymmetric dihydroxylation as the key step. A reversal of enantiofacial selectivity was observed in the asymmetric dihydroxylation.

Stereoselective Synthesis and Investigation of Isopulegol-Based Chiral Ligands.

A library of isopulegol-based bi-, tri- and tetrafunctional chiral ligands has been developed from commercially available (-)-isopulegol and applied as chiral catalysts in the addition of diethylzinc to benzaldehyde. Michael addition of primary amines towards α-methylene-γ-butyrolactone, followed by reduction, was accomplished to provide aminodiols in highly stereoselective transformations. Stereoselective epoxidation of (+)-neoisopulegol, derived from natural (-)-isopulegol, and subsequent oxirane ring opening with primary amines afforded aminodiols. The regioselective ring closure of N-substituted aminodiols with formaldehyde was also investigated. Hydroxylation of (+)-neoisopulegol resulted in diol, which was then transformed into aminotriols by aminolysis of its epoxides. Dihydroxylation of (+)-neoisopulegol or derivatives with OsO4/NMO gave neoisopulegol-based di-, tri- and tetraols in highly stereoselective reactions. The antimicrobial activity of aminodiol and aminotriol derivatives as well as di-, tri- and tetraols was also explored. In addition, structure-activity relationships were examined by assessing substituent effects on the aminodiol and aminotriol systems.