Glycosylidene Carbenes a new approach to glycoside synthesis. Part 1. Preparation of glycosylidene‐derived diaziridines and diazirines

Abstract

A new approach towards the synthesis of glycosides based upon a (formal) insertion of glycosylidene carbenes into 0-H bonds is presented. The synthesis and characterization of the glycosylidene-derived diazirines 25-28, precursors of glycosylidene carbenes, are described.

Glycosylidene Carbenes, Part 30, Crystal Structure of a Glucose-DerivedN,N-Unsubstituted Alkoxydiaziridine

“…The intermolecular interaction links the molecules into infinite one-dimensional chains that run parallel to the [001] direction and have a graph set motif of C(3). The trans configuration of the hydrazi group and the intramolecular H-bond are consistent with the conformation of the major diastereoisomer found in solution, as determined by NMR measurements [4].…”

Three‐Membered Heterocycles. Structure and Reactivity

“…Similarly, diaziridinimines such as 723 can be prepared in good yield by subjecting tosyl guanidine 722 to sequential treatment by t-butyl hypochlorite and t-butoxide [724]. the same method is effective in preparing the glycosylidene-derived diaziridine 727, which serves as a precursor for the corresponding diazirine and thus a glycosylidene carbene [726]. An operationally more straightforward variant of the methodology can be used for preparing various 2,2-disubstituted derivatives.…”

General Aspects of the Glycosidic Bond Formation

“…A new wave of methods arose in the end of the 1980s, among which were glycosyl donors such as glycosyl acyl/carbonates [36][37][38], thiocyanates [39], diazirines [40], xanthates [41], glycals [42,43], phosphites [44,45], sulfoxides [46], sulfones [47], selenium glycosides [48], alkenyl glycosides [49][50][51] and heteroaryl glycosides [52] (Figure 1.2). These developments were followed by a variety of more recent methodologies and improvements, among which are glycosyl iodides [53], phosphates [54], Te-glycosides [55], sulfonylcarbamates [56], disulfides [57], 2-(hydroxycarbonyl) benzyl glycosides [58] and novel thio- [59,60] and O-imidates [61,62] (Figure 1.2).…”