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.

Latex nanoparticles functionalized with cyclam (1,4,8,11-tetraazacyclotetradecane), a copper chelator, have been doped with a fluorescent dye (BODIPY derivative: 4,4-difluoro-8-(2',4',6'-trimethyl)phenyl-2,6-diethyl-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene). The bulky, hydrophobic fluorophore dissolves within the nanoparticles' polymer core up to a concentration of about 88.4 micromol g(-1). At this concentration the fluorescence yield is about 0.80. Adding Cu2+ ions to the solution decreases the fluorescence because of the energy transfer between the dye and the violet copper cyclam complexes. The response is fast: 90% of the quenching occurs within 1 s. The Cu2+ detection threshold is of 1 nanomolar. No interferences were observed with zinc and nickel ions.

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The cover picture shows how diisobutylaluminium hydride (DIBAL‐H), acting as a scalpel, is able to achieve a remarkably regioselective ablation of two benzyl groups out of the sixteen present in a fully benzylated α‐cyclodextrin molecule. This is assimilated in this pictorial attempt, created by Karine Leroy, to molecular surgery. Such a selective de‐O‐benzylating reaction is also applicable to perbenzylated carbohydrates. For more details about the accuracy of this unprecedented chemical operation, which delivers valuable alcohols in one step, see the article by M. Sollogoub, P. Sinaÿ et al. on p. 2960 ff.

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