Application of α-chloroaldoxime O-methanesulfonates to one-pot synthesis of N,N′,N″-substituted guanidines via Tiemann rearrangement

A Bifunctional Reagent Designed for the Mild, Nucleophilic Functionalization of Pyridines

“…With these criteria in mind, a class of imine-based reagents containing a leaving group at both the α-carbon and nitrogen were envisioned to promote the direct functionalization of pyridines. More specifically, α-chloro O -sulfonyl aldehyde oximes were targeted due to their ease of synthesis from aldehyde oximes with inexpensive reagents …”

Practical Synthesis of N-Substituted Cyanamides via Tiemann Rearrangement of Amidoximes

“…N -Substituted cyanamides or N , N ′-disubstituted carbodiimides have been shown to be the intermediates for the formation of ureas in the rearrangement . They are usually accompanied by subsequent reactions to form, for instance, N , N -disubstituted cyanamides (E), ureas (F), ,, or guanidines (G) and can be isolated only under certain conditions (C and D − ). There are a few exceptions where the rearrangement did not occur after the sulfonylation of amidoximes.…”

Guanidines from ‘toxic substances’ to compounds with multiple biological applications – Detailed outlook on synthetic procedures employed for the synthesis of guanidines

“…via Tiemann rearrangement (Figure 4a. ), involving the reaction of α-chloroaldoxime, o-methanesulfonateswith alkyl amines, was disclosed by Yamamoto in 2009 [65]. …”