1H NMR Analysis of the Metathesis Reaction between 1-Hexene and (E)-Anethole Using Grubbs 2nd Generation Catalyst: Effect of Reaction Conditions on (E)-1-(4-Methoxyphenyl)-1-hexene Formation and Decomposition

The metathesis of 1-hexene and (E)-anethole in the presence of Grubbs 2nd generation catalyst was monitored by in situ 1H NMR spectroscopy at different temperatures (15 °C, 25 °C, and 45 °C) and anethole mol fractions (XAnethole ≈ 0.17, 0.29, 0.5, 0.71, 0.83). Time traces confirmed the instantaneous formation of (E)-1-(4-methoxyphenyl)-1-hexene, the cross-metathesis product. A maximum concentration of (E)-1-(4-methoxyphenyl)-1-hexene is reached fairly fast (the time depending on the reaction conditions), and this is followed by a decrease in the concentration of (E)-1-(4-methoxyphenyl)-1-hexene due to secondary metathesis. The maximum concentration of (E)-1-(4-methoxyphenyl)-1-hexene was more dependent on the XAnethole than the temperature. The highest TOF (3.46 min−1) was obtained for the reaction where XAnethole was 0.16 at 45 °C. The highest concentration of the cross-metathesis product was however achieved after 6 min with an anethole mol fraction of 0.84 at 25 °C. A preliminary kinetic study indicated that the secondary metathesis reaction followed first order kinetics.

Recent advances in the synthesis of 5'-deoxynucleoside phosphonate analogs

: The present review focuses on the synthesis of cyclic 5-deoxynucleoside phosphonate analogs. The formation of various phosphonate alkyl moieties is accomplished through (i) Wittig (or HWE) type condensation to the nucleoside aldehyde moiety; (ii) nucleophilic displacement reaction using phosphonate anion or Lewis acid; (iii) Arbuzov reaction; (iv) olefin cross-metathesis between vinyl phosphonates and vinylated nucleosides; and (v) radical reaction and Pd catalyzed alkyne. For the coupling of nucleobases with cyclic moieties, the Mitsunobu reaction, and Sonogashira-type cross-coupling are usually applied. For the coupling of furanose moieties with nucleobases, Vorbrüggen-type condensation is generally applied. Addition reactions mediated by selenium ions are mainly applied for the coupling of carbocyclic moieties. Their biological activity results are summarized.