Self-promoted glycosylations with trichloroacetimidates have been described previously in the literature, and the first example was reported in 1980 by Schmidt and Michel namely the reaction between acetic acid and glucosyl trichloroacetimidate (Scheme 1). Carboxylic acids and phosphorus acid derivatives that can react as self-promoters are called A=B-C-H systems, named after the reactions presumed eight-membered (pseudo-sixmembered) transition state as illustrated in Scheme 1. Most of the self-promoted reactions described in the literature involve imidate or imidate-like donors, and a self-promotor that is acidic enough to protonate the basic imidate nitrogen. In the case of the A=B-C-H systems, the reaction is described as happening in one concerted step with protonation, attack of the anomeric carbon by the acceptor, and departure of the leaving group all occurring at the same time. However, by looking at the different acceptors in self-promoted reactions, it is evident that there are self-promoters, which do not fall into the A=B-C-H class. This includes the sulfonyl carbamates and phenol-like compounds. For both the A=B-C-H class of acceptors and the non-A=B-C-H class stereospecificity is observed, and some degree of memory of the donor configuration is kept. For the reaction of an α-glucosyl trichloroacetimidate (1-α Scheme 1) with an A=B-C-H system near full inversion is observed. Correspondingly for a β-glucosyl trichloroacetimidate (1-β scheme 1) full inversion to the α-glucoside is observed. For the reaction of an α-glucosyl trichloroacetimidate with a non-A=B-C-H acceptor near full inversion is also observed, albeit for the reaction of a non-A=B-C-H acceptor with a β-glucosyl trichloroacetimidate moderate to no selectivity is observed. We, therefore, set out to investigate the mechanism of self-promoted glycosylations with non-A=B-C-H-like self-promotors, as we wanted to get a better understanding of the scope and limitation of these types of reactions. The reaction takes place under ambient mild conditions. No catalyst or promoter is added so the atom economy is good, as the only byproduct is the trichloroacetamide, hence it is desired to broaden the scope, and eventually design new self-promoters using the mechanistic understanding gained in this study. In addition, our understanding of these types of reactions recently led to the discovery of pyrylium salts as catalysts for stereospecific O-glycosylations. Through coordination with the alcohol hydrogen, the pyrylium salts are capable of lowering the pK a of alcohols, enough for enabling protonation of the imidate nitrogen, thereby creating an in-situ "self-promoter" (Scheme 1). In this paper, we present a proposed mechanism for self-promoted N -glycosylations based on both kinetic data, computational studies, and nucleophile competition experiments.