"[9A587656FACF]" . . "From homoallenyl aldehydes to proton sponges"@en . . "2"^^ . "Pot\u00E1\u010Dek, Milan" . . . "From homoallenyl aldehydes to proton sponges"@en . "14310" . "2"^^ . "From homoallenyl aldehydes to proton sponges" . . . . "RIV/00216224:14310/12:00057492" . "allenyl aldehyde - rearrangement - proton sponge - basicity"@en . . . "Herein, we report a molecular framework design differing significantly from the traditional topology of proton sponges. We developed a suitable synthetic approach to the preparation of compounds with four fused five-membered rings from homoallenyl aldehydes by intramolecular criss-cross cycloaddition reactions of appropriate homoallenyl azines. The acid-catalyzed rearrangement of these cycloadducts afforded caged bidentate secondary amines in quantitative yields and following alkylation reactions led to final air nonsensitive highly stable substituted diazatetracyclo[4.4.0.13,10.15,8]dodecanes (DTDs) with rare alicyclic scaffolding in high overall yields. These molecules have two pairs of nitrogen atoms fixed in a configuration that guarantees acid-base properties similar to those of proton sponges. Their pKBH+ values were determined by 1H NMR transprotonation experiments as well as their sensitivity toward nucleophiles, acids and bases."@en . "Herein, we report a molecular framework design differing significantly from the traditional topology of proton sponges. We developed a suitable synthetic approach to the preparation of compounds with four fused five-membered rings from homoallenyl aldehydes by intramolecular criss-cross cycloaddition reactions of appropriate homoallenyl azines. The acid-catalyzed rearrangement of these cycloadducts afforded caged bidentate secondary amines in quantitative yields and following alkylation reactions led to final air nonsensitive highly stable substituted diazatetracyclo[4.4.0.13,10.15,8]dodecanes (DTDs) with rare alicyclic scaffolding in high overall yields. These molecules have two pairs of nitrogen atoms fixed in a configuration that guarantees acid-base properties similar to those of proton sponges. Their pKBH+ values were determined by 1H NMR transprotonation experiments as well as their sensitivity toward nucleophiles, acids and bases." . "RIV/00216224:14310/12:00057492!RIV13-GA0-14310___" . . . "137298" . . "P(GA203/09/1345)" . "From homoallenyl aldehydes to proton sponges" . . "Galeta, Juraj" . . .