Proton sponges-based (2-naphthyl)pyridylmethanol

Superbasic Alkyl‐Substituted Bisphosphazene Proton Sponges: Synthesis, Structural Features, Thermodynamic and Kinetic Basicity, Nucleophilicity and Coordination Chemistry

“…The so-called buttressing effect describes the substitution of the 2-and 7-position by preferably electron-rich and bulky groups further destabilizing the unprotonated proton sponge by enforcing an even stronger repulsion of the nitrogen atoms' lone pairs. [16] Another possible modification of naphthalene-based proton sponges is the variation of the substituents at the basicity centers. Besides the replacement of DMAN's methyl groups by numerous different alkyl substituents, [17][18][19] the nitrogen atoms have been integrated in an aromatic system as for instance shown in Staab's quino- [7,8h]quinoline.…”

1,8,1′,8′-Tetrakis(dimethylamino)-2,2′-dinaphthylmethanols: DoubleIn/OutProton Sponges with Low-Barrier Hydrogen-Bond Switching

“…It has been previously disclosed that placing almost any substituent in the ortho -positions of 1,8-bis(dimethylamino)naphthalene (“proton sponge”, 1 ) influences, often dramatically, its structure, − basicity, ,, and reactivity. , For example, whereas the parent compound 1 and the vast majority of its derivatives normally exist as in/in conformers with the free NMe 2 electron pairs pointing toward each other, for 2,7-bis(trimethylsilyl)derivative the nonconventional in/out form 2 becomes dominant. , Recently, we have demonstrated that fixation of the in/out form can be organized via intramolecular hydrogen bonding (IHB) between the NMe 2 and tertiary α-hydroxymethyl groups as in 3 . Unlike this, primary and secondary o - mono- and dialcohols prefer in/in conformation in which the OH groups participate in the formation of ···OH···OH··· associates , (cf. also ref ).…”