Molecular Scissors for Tailor‐Made Modification of Siloxane Scaffolds

The controlled design of functional oligosiloxanes is an important topic in current research. A consecutive Si−O−Si bond cleavage/formation using siloxanes that are substituted with 1,2‐diaminobenzene derivatives acting as molecular scissors is presented. The method allows to cut at certain positions of a siloxane scaffold forming a cyclic diaminosilane or ‐siloxane intermediate and then to introduce new functional siloxy units. The procedure could be extended to a direct one‐step cleavage of chlorooligosiloxanes. Both siloxane formation and cleavage proceed with good to excellent yields, high regioselectivity, and great variability of the siloxy units. Control of the selectivity is achieved by the choice of the amino substituent. Insight into the mechanism was provided by low temperature NMR studies and the isolation of a lithiated intermediate.