Nature provides synthetic organic chemists with several challenges in the form of complex natural products. These metabolites often exhibit remarkable biological activity such as antitumoral, antimicrobial, amongst others. A variety of these biologically active natural products share a common aminocyclopentane core. These have been isolated from various sources such as the plant Alstonia macrophylla (indole alkaloids) , the bacteria Streptomyces pactum (pactamycin, pactamycate, jogyamycin) , and from deep sea marine sponges of the genus Agelas (nemoechine A , agelamadins and agelastatins ) as depicted in Figure . Despite the pharmacological importance of these compounds, poor availability hinders drug development endeavors. For this reason, the scientific community has tackled this issue by performing the total synthesis of the active metabolites, hence bypassing the availability concerns. Moreover, the synthetic challenge of creating these complex natural products have inspired many groups to develop novel technologies transversal to other scientific communities. Due to the increased availability of synthetic Agelastatin A (AglA), the mechanism for its cytotoxicity was recently elucidated , highlighting the importance of total synthesis. The study by Liu and coworkers identified the eukaryotic ribosome as a cellular target of AglA using a systematic top-down approach, culminating in a co-crystallization of the alkaloid and 80S eukaryotic ribosome from S. cerevisiae. Several strategies have been employed for the formation of the cyclopentane core, such as bond insertion of an alkylidenecarbene, metathesis reaction, imidazolone-forming annulation reaction followed by a carbohydroxylative trapping of imidazolones, polar 5-exo-trig cyclization amongst others. Concerning the introduction of the amine moieties, often aziridination is used to introduce both an amine and a carbon electrophilic center to undergo further amination. Additionally, other approaches involve conjugate additions, palladium-catalyzed asymmetric allylic alkylation (AAA), [3,3]-sigmatropic rearrangement of cyanates, and Mitsunobu reaction. In an attempt to reduce the number of steps towards the final products, Batey and coworkers designed an elegant approach in which a single operational step delivered a diamino carbocycle used in the total synthesis of AglA by. To this end, the authors optimized the formation of trans-4,5-diaminocyclopentenones (DCPs) from biomass derived furfural promoted by dysprosium trifluoromethanosulfonate under mild conditions, which have been further studied by several research groups (Figure ). One DCP was used as diaminocyclopentane synthon through deprotection of the diallylamine group. Despite the concomitant reduction of reaction steps and increase in yield provided by the one step introduction of the two amines and formation of the carbocycle, a major challenge of this approach is the differentiation of the two primary amines formed upon deprotection of the DCP. The authors overcame this issue via a selective coupling of bromopyrrole lithium carboxylate and one of the primary amines. Inspired by this approach, we envisioned that the preparation of orthogonally protected DCPs would allow sequential modification of the amines, broadening the toolbox of the DCP system as synthons for the preparation of other diaminocyclopentane natural products and AglA analogues, in particular with different amine substituents (Figure ). The reversibility of cyclopentenone -Stenhouse salts, despite uncommon on DCP, has been thoroughly studied in cyclopentenonedonor-aceptor Stenhouse adducts (DASA) systems developed by Alaniz and coworkers. Aligned with previous findings where DCP stock solutions appeared to be contaminated with furfural upon HPLC-UV analysis, we pursued the possibility of amine exchange in established cyclopentenones promoted by this equilibrium. To this end, a mixture of DCP obtained from furfural and morpholine was stirred with 2 equivalents of dibenzylamine, in the presence of Cu(OTf)2. After 30 minutes a new product was identified as mixed CP 1a. (Figure ) Further studies, including NOESY experiments of other mixed DCP, suggest the regioselective addition of morpholine in position 4 and dibenzylamine in position 5 (See SI). However, if the mixture was allowed to react longer to achieve full consumption of the initial DCP, a secondary product was obtained, consisting of the known 2,4-isomer cyclopentenone obtained by Aza-Michael addition of dibenzylamine followed by elimination of the amine to reform the enone system (Figure ). This observation prompted us to react furfural under our previous reported conditions, in the presence of stoichiometric amounts of dibenzylamine and morpholine. Upon isolation, the mixed CP 1a was isolated as a minor product in 38% yield (Table , Entry 1), with the majority of the mass balance being the bisdibenzylamine DCP. The reaction was optimized by screening different solvents, reaction times and amine equivalents. The optimal conditions were identified as 1 equivalent of dibenzylamine and 2 equivalents of morpholine and furfural under aqueous conditions for 5 minute (Table , Entry 3). If the reaction is allowed to stir for longer (15 minutes) the yield decreases (Table , Entry 4). Attempts at changing the Lewis acid did not afford the desired product, with the exception of Erbium triflate which afforded 1a in 28 % yield. Using organic solvents lead to decomposition and no DCP was isolated (Table , Entry 5). Diluting the reaction to 0.1 M concentration reduced the yield to 47 %(Table , Entry 6). 3 5 H2O 2 72