Oxocarbenium ions 2-deoxyglucosyl

The solvolysis of 2-deoxyglucopyranosides has been studied extensively by the Bennet laboratory with emphasis on the progression through the dissociative mechanistic continuum and characterization of the lifetime of the 2-deoxyglucosyl oxocarbenium ion. 

Solvolysis of 2-deoxyisoquinolinium salts in the presence of azide does not show AnDn kinetic behavior, and the 2-deoxyglucosyl oxocarbenium ion is not solvent... 

As a result of these studies, and the approximately 4-fold greater stability attributed to 2-deoxyglycosyl oxocarbenium ions over their 2-hydroxy counterparts, Zhu and Bennet estimated that the lifetime for the 2-deoxyglucosyl oxocarbenium ion is on the order of 2 x 10-11 s, and 10—12 s for the glucosyl oxocarbenium ion in water, consistent with prior results.29... 

The barrier for capture of the 2-deoxyglucosyl oxocarbenium ion (24->26) is lJkcalmor1 while for the neuraminyl ion (25->27) the barrier is. I kcalmol-1 both of these values were corrected for zero-point energy. These results agree with experiments that indicated the NeuAc oxocarbenium ion is marginally more stable than the 2-deoxyglucosyl oxocarbenium ion. 

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