Bart Steenackers

Chemical transformations of characteristic hop secondary metabolites in relation to beer properties and the brewing process: A review

The annual production of hops (Humulus lupulus L.) exceeds 100,000 mt and is almost exclusively consumed by the brewing industry. The value of hops is attributed to their characteristic secondary metabolites; these metabolites are precursors which are transformed during the brewing process into important bittering, aromatising and preservative components with rather low efficiency. By selectively transforming these components off-line, both their utilisation efficiency and functionality can be significantly improved. Therefore, the chemical transformations of these secondary metabolites will be considered with special attention to recent advances in the field. The considered components are the hop alpha-acids, hop beta-acids and xanthohumol, which are components unique to hops, and alpha-humulene and beta-caryophyllene, sesquiterpenes which are highly characteristic of hops.

The strained sesquiterpene β-caryophyllene as a probe for the solvent-assisted epoxidation mechanism.

In our attempt to synthesize β-caryophyllene oxide in food-compatible conditions, we observed the uncatalyzed and highly selective epoxidation of β-caryophyllene, a strained bicyclic sesquiterpene, in ethanol with aqueous H2 O2 under radical-suppressing conditions without the addition of a catalyst. The unusual reactivity of β-caryophyllene allowed us to use it as a probe for the mechanism of the solvent-assisted epoxidation in a wide range of organic solvents. A kinetic study was performed to investigate the epoxidation mechanism; an excellent correlation was found between the observed epoxidation rates in different solvents and the Abrahams hydrogen bond formation parameters of these solvents. By means of computational analysis, it was found that the main role of the solvent consists of the stabilization of the elongated OO bond of H2 O2 in the transition state through hydrogen-bond donation to the leaving OH moiety of H2 O2 . α-Humulene was found to possess similar reactivity as β-caryophyllene whereas isocaryophyllene-the unstrained isomer of β-caryophyllene-was unreactive.

Electron Transfer‐Initiated Epoxidation and Isomerization Chain Reactions of β‐Caryophyllene

The abundant sesquiterpene β-caryophyllene can be epoxidized by molecular oxygen in the absence of any catalyst. In polar aprotic solvents, the reaction proceeds smoothly with epoxide selectivities exceeding 70 %. A mechanistic study has been performed and the possible involvement of free radical, spin inversion, and electron transfer mechanisms is evaluated using experimental and computational methods. The experimental data-including a detailed reaction product analysis, studies on reaction parameters, solvent effects, additives and an electrochemical investigation-all support that the spontaneous epoxidation of β-caryophyllene constitutes a rare case of unsensitized electron transfer from an olefin to triplet oxygen under mild conditions (80 °C, 1 bar O2 ). As initiation of the oxygenation reaction, the formation of a caryophyllene-derived radical cation via electron transfer is proposed. This radical cation reacts with triplet oxygen to a dioxetane via a chain mechanism with chain lengths exceeding 100 under optimized conditions. The dioxetane then acts as an in situ-formed epoxidizing agent. Under nitrogen atmosphere, the presence of a one-electron acceptor leads to the selective isomerization of β-caryophyllene to isocaryophyllene. Observations indicate that this isomerization reaction is a novel and elegant synthetic pathway to isocaryophyllene.