Allylic azides: synthesis, reactivity, and the Winstein rearrangement

Abstract

Allylic azides are useful synthetic intermediates, the Winstein rearrangement complicates usage, and mechanistic knowledge can enable selectivity.

Triazoles with long chain alkyl groups as a potential biological compounds

“…in pyridine (20 mL) was added for acetylating. Recrystallization with ethanol was done to produce NMR pure white crystal of compound [3] in very good yield (Carlson and Topczewski, 2019;Kantaria et al, 2018;Hajipour and Ghorbani, 1920;Costa et al, 2017).…”

Crystal structures of 4-{(E)-3-[(imino-λ5-azanylidene)amino]prop-1-enyl}-N,N-dimethylimidazole-1-sulfonamide and 2-[(imino-λ5-azanylidene)amino]-4-{(E)-3-[(imino-λ5-azanylidene)amino]prop-1-enyl}-N,N-dimethylimidazole-1-sulfonamide

“…The efficient synthesis of nagelamide alkaloids (a subfamily of oroidin natural products derived from marine sponges) has garnered interest (Du et al, 2006;Das et al, 2016) since first reported (Endo et al, 2004). Allylic azides (Carlson & Topczewski, 2019) are fairly reactive making them attractive starting compounds to convert into amides. Our group has successfully synthesized a number of azide-containing imidazole derivatives and determined their structures.…”

Insight on the Factors Controlling the Equilibrium of Allylic Azides

“…[7][8][9][10] Allylic azides are building blocks for the synthesis of natural products and nitrogen-containing heterocycles of pharmacological relevance. [11][12][13][14] Despite the importance of these useful synthons, their applicability in synthetic schemes has been difficult due to their existence as a regioisomeric mixture that interconverts rapidly at room temperature, being in general inseparable (Figure 1). 15,16 The allylic azide rearrangement was first reported by Gagneux, Winstein, and Young in 1960 (known as Winstein's rearrangement).…”