Diastereochemical differentiation of bicyclic diols using metal complexation and collision-induced dissociation mass spectrometry.

Metal complex formation was investigated for di-exo-, di-endo- and trans-2,3- and 2,5-disubstituted trinorbornanediols, and di-exo- and di-endo- 2,3-disubstituted camphanediols using different divalent transition metals (Co(2+), Ni(2+), Cu(2+)) and electrospray ionization quadrupole ion trap mass spectrometry. Many metal-coordinated complex ions were formed for cobalt and nickel: [2M+Met](2+), [3M+Met](2+), [M-H+Met](+), [2M-H+Met](+), [M+MetX](+), [2M+MetX](+) and [3M-H+Co](+), where M is the diol, Met is the metal used and X is the counter ion (acetate, chloride, nitrate). Copper showed the weakest formation of metal complexes with di-exo-2,3-disubstituted trinorbornanediol yielding only the minor singly charged ions [M-H+Cu](+), [2M-H+Cu](+) and [2M+CuX](+). No clear differences were noted for cobalt complex formation, especially for cis-2,3-disubstituted isomers. However, 2,5-disubstituted trinorbornanediols showed moderate diastereomeric differentiation because of the unidentate nature of the sterically more hindered exo-isomer. trans-Isomers gave rise to abundant [3M-H+Co](+) ion products, which may be considered a characteristic ion for bicyclo[221]heptane trans-2,3- and trans-2,5-diols. To differentiate cis-2,3-isomers, the collision-induced dissociation (CID) products for [3M+Co](2+), [M+CoOAc](+), [2M-H+Co](+) and [2M+CoOAc](+) cobalt complexes were investigated. The results of the CID of the monomeric and dimeric metal adduct complexes [M+CoOAc](+) and [2M-H+Co](+) were stereochemically controlled and could be used for stereochemical differentiation of the compounds investigated. In addition, the structures and relative energies of some complex ions were studied using hybrid density functional theory calculations. Copyright (c) 2009 John Wiley & Sons, Ltd.