Two Different Selective Ways in the Deprotonation of β‐Bromopropionanilides: β‐Lactams or Acrylanilides Formation.

Abstract

The reactivity of 3‐bromo‐N‐(p‐bromophenyl)propanamide with different bases in an ionic liquid (BMImBF4) and in acetonitrile (ACN) was studied. Two possible deprotonation sites are present in this molecule, leading to different products. When the NH group is deprotonated, a β‐lactam is obtained after internal halide displacement; when the CH2 in alpha to the carbonyl is deprotonated, the corresponding acrylanilide is formed. This study allowed determining the experimental conditions to obtain selectively and in high yields both products starting from the same molecule. In particular, to obtain the acrylanilide Et3N in ACN is to be used, while to obtain selectively the β‐lactam ring the base must be generated by cathodic reduction of a DMF or ACN‐Et4NBF4 solution. These reactions were extended to other β‐bromopropionanilides, allowing to easily synthesize both β‐lactams and acrylanilides, molecules having noteworthy biological activities.

An Insight into the Reactivity of the Electrogenerated Radical Cation of Caffeine

“…In this regard, the electrochemical reduction of CAF in organic solvent has been recently reported, the methodology leading to an amino-functionalized imidazole, not chemically obtainable, with valuable applications in organic synthesis [17,18]. It is in fact well known that in some cases electrochemistry can lead to different products than those obtained by classical chemical reactions [19].…”

WO3 and Ionic Liquids: A Synergic Pair for Pollutant Gas Sensing and Desulfurization

“…Notwithstanding the plethora of different applications, the use of ILs as reaction media is probably the most widely applied and investigated [65][66][67][68][69][70]. They have been used to perform classical organic reactions, such as nucleophilic aromatic substitution, elimination reaction, ring to ring interconversion in heterocyclic systems, cycloaddition reaction and so on [71][72][73][74][75][76][77]. This endows them with low vapor pressure and flammability and high thermal stability.…”

Synthesis of β-Lactams through Carbonylation of Diazo Compounds Followed by the [2 + 2] Cycloaddition Reaction

“…31 Feroci et al explained an electrochemical strategy where deprotonation β-bromopropionanilide at the N−H position (alpha to the carbonyl group) followed by internal bromide displacement produced βlactam. 32 Synofzik et al suggested the reaction of α-acyl-αdiazoacetates with imines under reflux condition, yielding βlactams. The reflux condition directs the generation of the carbene homo-coupled product, resulting in less yield of the desired product.…”

“…reported α-hydroxylation of sulfonylcyclopropanes to form cyclopropanone, which further undergoes [3 + 1] cycloaddition with hydroxylamines to produce chiral β-lactams (Figure c) . Feroci et al explained an electrochemical strategy where deprotonation β-bromopropionanilide at the N–H position (alpha to the carbonyl group) followed by internal bromide displacement produced β-lactam . Synofzik et al suggested the reaction of α-acyl-α-diazoacetates with imines under reflux condition, yielding β-lactams.…”