Several commercially available lipases were examined in a study on O–Si bond formation and cleavage applying silicon-based protecting groups and alcohols or the corresponding silyl ethers. With regard to deprotection, from silyl ether to the corresponding alcohol, only the solvent and the lipase were necessary. The influence of the protecting group, the lipase source, and the substituent was investigated to optimize the results. The TMS moiety could be removed in 24 hours of reaction at room temperature in aqueous systems (conv. up to 99%, depending on the substrate and lipase). The reverse reactions, that is, with the protection of the alcohols, were carried out in hexane using different silyl chlorides. The TMS, TES, and TBS moieties were successfully inserted in the primary and secondary alcohols without the need for dry conditions or an inert atmosphere, presenting conversions of up to 99%, depending on the substrate.

The protection reactions of alcohols (primary and secondary) were efficiently performed applying silyl chlorides (Me3SiCl, Et3SiCl, t‐BuMe2SiCl and t‐BuPh2SiCl) as protecting source, on grinding, without the use of a catalyst. The reactions proceeded smoothly, either at room temperature or at 40 °C, depending on the protecting group applied, and under solvent‐free conditions. In comparison with the classical reaction conditions, which employ, most of the times, solvent in anhydrous conditions (tetrahydrofuran or N,N‐dimethylformamide), this synthetic protocol exhibits the advantages of shorter reaction times, milder reaction conditions, higher yields and simpler purification steps. Under this method 21 examples could be obtained at short reaction times (5 – 10 min) and presenting up to 98% of yields. When the substrate was a diol bearing primary and phenolic hydroxyl moieties, the monoprotected or the diprotected product could be obtained as a sole product, in excellent yields.

Few works present effective or viable alternatives to the problem of the electroreduction of acetophenone which usually leads to the pinacol dimer as a primary product in addition to 1‐phenylethanol. Here, various lipases were applied in acetophenone electroreduction. The optimized reaction conditions are tin/lead (63 : 37) combined working electrode coated with Nafion film modified with lipase from Thermomyces lanuginosus, a platinum counter electrode, applied potential of −2.0 V vs. Ag/AgCl (KCl 3.0 mol L−1), acetate buffer (0.1 mol L−1) pH 5.0 in 4 hours, and led to the formation of 87.8 % of 1‐phenylethanol. The same working electrode was used five times over five days, and the conversion remained constant. A voltammetric study indicates an alteration of the electroreduction mechanism in the presence of the cited lipase. Adding lipase from Thermomyces lanuginosus directly in the medium immobilized in a clay mineral or in silica gel (Lipolase 100T) resulted in even higher conversions (93.2–93.9 %). The modified electrode improved the methodology regarding enzyme stability, process reproducibility, and material reusability.