To explain the remarkable regioselective de-O-benzylating properties of diisobutylaluminium hydride (DIBAL-H) and triisobutylaluminium (TIBAL) towards polybenzylated sugars or cyclodextrins, we propose a plausible mechanistic rationale critically involving the kinetic formation of a product-generating 2:1 Al-benzylated sugar complex. For the reaction to occur, one pair of adjacent oxygen atoms should first be able to form a chelation complex with the first equivalent of aluminium reagent, either a highly fluxional complex with tetracoordinate aluminium species or a pentacoordinate one. The second equivalent then induces the regioselectivity of the de-O-alkylation by coordinating preferentially to one of the oxygen atoms of the selected pair.

Al together now: Aluminotriazoles are obtained in a fully chemo‐ and regioselective manner by a copper‐catalyzed cycloaddition of organic azides with mixed‐aluminum acetylides (see scheme). The carbonaluminum bond, which is unaffected by the first transformation, is still able to react further with different electrophiles.