Stereoselective β-Hydrogen Elimination from Nickel(II)−N-Glycoside Complexes
- 1 April 1997
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 62 (7) , 2152-2154
- https://doi.org/10.1021/jo9622789
Abstract
Octahedral nickel(II)−N-glycoside complexes of glucose, galactose, mannose, and talose were synthesized and analyzed by electrospray ionization (ESI). A resulting tricoordinate species generated from the octahedral complex was subjected to collision-induced dissociation. A highly stereoselective dissociation pathway involving β-hydrogen elimination and cross-ring cleavages was observed in complexes possessing equatorial C-2 substituents. 2H- and 13C-labeling experiments indicate that the hydrogen on C-2 and a labile proton are involved in the β-hydrogen elimination. Additionally, C-4, C-5, and C-6 are shown to be lost from the monosaccharide as a result of the cross-ring cleavages. A mechanism is postulated to explain the stereoselectivity of this dissociation.Keywords
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