Compared to the biological world's rich chemistry for functionalizing carbon, enzymatic transformations of the heavier homologue silicon are rare. We report that a wild‐type cytochrome P450 monooxygenase (P450BM3 from Bacillus megaterium, CYP102A1) has promiscuous activity for oxidation of hydrosilanes to give silanols. Directed evolution was applied to enhance this non‐native activity and create a highly efficient catalyst for selective silane oxidation under mild conditions with oxygen as the terminal oxidant. The evolved enzyme leaves C−H bonds present in the silane substrates untouched, and this biotransformation does not lead to disiloxane formation, a common problem in silanol syntheses. Computational studies reveal that catalysis proceeds through hydrogen atom abstraction followed by radical rebound, as observed in the native C−H hydroxylation mechanism of the P450 enzyme. This enzymatic silane oxidation extends nature's impressive catalytic repertoire.

The combination of electrophilic and nucleophilic reaction partners can be an obvious approach toward the formation of C­(sp3)–Si bonds. Regioselectivity issues are avoided as the locus of bond formation is set in the prefunctionalized alkyl coupling partner. However, synthetically useful protocols only evolved in recent years, closing an important gap in silicon chemistry. This Perspective summarizes early efforts for the construction of C­(sp3)–Si bonds and highlights the recent catalytic approaches either utilizing electrophilic or nucleophilic silicon reagents. The underlying reaction mechanisms range from ionic or radical cross-couplings to simple nucleophilic substitution.

Electrophilic aromatic substitution is a fundamental reaction in synthetic chemistry. It converts C-H bonds of sufficiently nucleophilic arenes into C-X and C-C bonds using either stoichiometrically added or catalytically generated electrophiles. These reactions proceed through Wheland complexes, cationic intermediates that rearomatize by proton release. Hence, these high-energy intermediates are nothing but protonated arenes and as such strong Brønsted acids. The formation of protons is an issue in those rare cases where the electrophilic aromatic substitution is reversible. This situation arises in the electrophilic silylation of C-H bonds as the energy of the intermediate Wheland complex is lowered by the β-silicon effect. As a consequence, protonation of the silylated arene is facile, and the reverse reaction usually occurs to afford the desilylated arene. Several new approaches to overcome this inherent challenge of C-H silylation by S Ar were recently disclosed, and this Minireview summarizes this progress.

The activation of perfluoroalkyl iodides by the frustrated Lewis pair tris(pentafluorophenyl)borane and tri-tert-butylphosphine is described. By abstraction of both a fluorine and an iodine atom, an iodophosphonium fluoroborate salt is formed. In the presence of alkenes the corresponding iodoperfluoroalkylation products are generated regioselectively. First mechanistic investigations support a radical mechanism.