Acidifying Effect of an N-Oxide Group - A Useful Motif in Enhancing Acidity towards Superacidic Values

Vianello, Robert (2009) Acidifying Effect of an N-Oxide Group - A Useful Motif in Enhancing Acidity towards Superacidic Values. Croatica Chemica Acta, 82 (1). pp. 27-39. ISSN 0011-1643

PDF - Published Version
Download (2MB)

Official URL: http://hrcak.srce.hr/index.php?show=clanak&id_clan...

Abstract

DFT calculations carried out on trams-decahydronaphthalene and 4b,8b-dihydronaphthalene, important structural features of many alkaloids, revealed that they are moderately acidic carbon acids in the gas-phase and in DMSO solution. Substitution with a nitrogen atom of a neighbouring C(sp(3))-H fragment bonded to an acidic centre reduces the corresponding acidity in both phases. Following that, oxidation of the nitrogen atom to an N-oxide group enhances the acidity significantly. This acidifying effect of an N-oxide moiety in the vicinity of a deprotonation centre was estimated to be around 9-17 kcal mol(-1) in the gas-phase deprotonation enthalpy and about 5-11 pK(a) units in DMSO. Therefore, this electronic effect could be applied in the design of novel strong acids and superacids. Such acidity enhancement is identified through triadic analysis to be a consequence of the final state effect of anion, where compounds bearing an N-oxide group benefit from the favourable charge-dipole interaction between the negative charge and an N-O group. A dramatic increase in acidity is observed upon multiple cyanation. For example, octacyanoquinolizine N-oxide is an extremely strong superacid as seen by the gas-phase Delta H(acid) = 254.8 kcal mol(-1) and pK(a,DMSO) = -20.2, and its synthesis is highly desirable and strongly recommended. Triadic analysis suggests that this huge acidifying effect takes place because of strong resonance in anions of polycyano compounds, efficiently assisted by multiple CN groups, which stabilizes the corresponding principal molecular orbitals.

Item Type:

Article

Uncontrolled Keywords:

triadic analysis; deprotonation; isodensity polarized continuum model; pK(a) value; superacids; gas-phase acidities; rees polycyanated hydrocarbons; palladium-catalyzed cyanation; dimethyl-sulfoxide solution; weakly coordinating anions; neutral organic superacids; density-functional theory; computational dft methods; ab-initio; bronsted acids

Subjects:

NATURAL SCIENCES > Chemistry

Divisions:

Division of Organic Chemistry and Biochemistry

Projects: