The photosensitized p-anisaldehyde-mediated addition of sulfonylcyanides onto the π-system of cyclobutenes is shown to afford highly functionalized cyclobutanes in high yields and diastereocontrol. The homochiral cyclobutene precursors are accessible on multigram scale in two steps through an asymmetric [2 + 2] cycloaddition/vinyl thioether reduction sequence. The enantiopure cyclobutylnitriles can be elaborated further through SmI2-mediated ring opening or converted into new enantiopure cyclobutenes through base-mediated sulfone elimination.

We have developed a convenient and versatile synthetic methodology to prepare various azidoorganotrialkoxysilanes using the platinum‐catalyzed hydrosilylation of stable olefinic precursors with an azide function as the last step. Hydrosilylation of alkene‐functionalized aliphatic and aromatic azides featuring alkyl, urea, carbamate and pegylated moieties has been successfully achieved while preserving the integrity of the azide function. The spin coating technique has been used successfully to prepare one azide‐terminated monolayer in ambient atmosphere onto an oxide surface. This process has the advantages of being fast, simple, easy to handle and needs less solvent. The ability of the azide‐terminated surface to immobilize molecules via the copper‐catalyzed alkyne‐azide cycloaddition reaction has been demonstrated by Modulation Infrared Reflection‐Adsorption Spectroscopy using a probe molecule bearing a NO2 group.