Transition Metal-Free Generation of N-Unsubstituted Imines from Benzyl Azides: Synthesis of N-Unsubstituted Homoallylic Amines

Abstract

An efficient transition metal-free approach for the generation of N-unsubstituted imines from azides followed by trapping with allyl nucleophile to provide N-unsubstituted homoallylic amines has been described. Although catalytic KO(t)Bu in DMSO is sufficient to allow imine generation, stoichiometric KO(t)Bu is essential in THF. Further, an enantio- and diastereoselective synthesis of homoallylic amines from benzyl azide has also been exemplified.

Chemical Modification of Poly(Vinyl Alcohol) in Water

“…Moreover, the presence of azide moiety is of considerable utility in the generation of other functionalities, e.g., amines via reduction, imines via rearrangement, triazoles and other heterocycles via cycloaddition [13][14][15]. Herein, we investigate the use of water as solvent during the azidation reaction.…”

Allylic azides: synthesis, reactivity, and the Winstein rearrangement

“…The most well-established method to access allylic azides is through nucleophilic substitution with sodium azide (Schemes 1a and 2a). [49][50][51][52][53][54][55] Allylic systems are typically activated for substitution and a wide range of electrophiles undergo substitution with azide anion including halogens, sulfonates, and some activated esters (Scheme 2a). As expected for a nucleophilic substitution, this reaction typically occurs with inversion of configuration.…”

“…Imine formation was followed by an allylation (Scheme 23c). 51 In this case, the aryl group stabilizes the conjugated alkene isomer, which controls the Winstein rearrangement. A high yield of the allyl amine was attained for most substrates.…”

Generation of N–H Imines from α-Azidocarboxylic Acids through Ru-Catalyzed Decarboxylation

“…Again, these procedures exhibit low functional group tolerance because of high reactivity of the organometallic compounds . In addition, the Ghorai group reported a synthesis of N–H imines from azides under metal-free conditions in the presence of a strong base KO t Bu . Although this procedure was successfully applied to a number of secondary benzylic azides, aliphatic azides could not be converted to the corresponding imines.…”