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Despite being very productive, the lack of selectivity and the reduced number of viable transformations restrict their general application in synthesis. Hereby, we describe a rationale for a selective version of these processes based in the preferential generation of intermediates which are less reactive than the initial substrates. In this way, applying the Groebke\u2013Blackburn\u2013Bienaym\u00e9 reaction on a range of \u03b1\u2010polyamino\u2010polyazines, we prepared a family compact heterocyclic scaffolds with relevant applications in medicinal and biological chemistry (live cell imaging probes, selective binders for DNA quadruplexes, and antiviral agents against human adenoviruses). The approach has general character and yields complex molecular targets in a selective, tunable and direct manner.<\/jats:p>","DOI":"10.1002\/chem.201802877","type":"journal-article","created":{"date-parts":[[2018,7,5]],"date-time":"2018-07-05T08:11:44Z","timestamp":1530778304000},"page":"14513-14521","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":53,"title":["Multiple Multicomponent Reactions: Unexplored Substrates, Selective Processes, and Versatile Chemotypes in Biomedicine"],"prefix":"10.1002","volume":"24","author":[{"given":"Ouldouz","family":"Ghashghaei","sequence":"first","affiliation":[{"name":"Laboratory of Medicinal Chemistry, Faculty of Pharmacy and Institute of, Biomedicine (IBUB) University of Barcelona  Barcelona Science Park, Baldiri Reixac 10\u201312 Barcelona 08028 Spain"},{"name":"CIBER-BBN, Networking Centre for Bioengineering, Biomaterials &amp; Nanomedicine  Baldiri Reixac 10\u201312 Barcelona 08028 Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Samantha","family":"Caputo","sequence":"additional","affiliation":[{"name":"Laboratory of Medicinal Chemistry, Faculty of Pharmacy and Institute of, Biomedicine (IBUB) University of Barcelona  Barcelona Science Park, Baldiri Reixac 10\u201312 Barcelona 08028 Spain"},{"name":"CIBER-BBN, Networking Centre for Bioengineering, Biomaterials &amp; Nanomedicine  Baldiri Reixac 10\u201312 Barcelona 08028 Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Miquel","family":"Sintes","sequence":"additional","affiliation":[{"name":"Laboratory of Medicinal Chemistry, Faculty of Pharmacy and Institute of, Biomedicine (IBUB) University of Barcelona  Barcelona Science Park, Baldiri Reixac 10\u201312 Barcelona 08028 Spain"},{"name":"CIBER-BBN, Networking Centre for Bioengineering, Biomaterials &amp; Nanomedicine  Baldiri Reixac 10\u201312 Barcelona 08028 Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marc","family":"Rev\u00e9s","sequence":"additional","affiliation":[{"name":"Laboratory of Medicinal Chemistry, Faculty of Pharmacy and Institute of, Biomedicine (IBUB) University of Barcelona  Barcelona Science Park, Baldiri Reixac 10\u201312 Barcelona 08028 Spain"},{"name":"CIBER-BBN, Networking Centre for Bioengineering, Biomaterials &amp; Nanomedicine  Baldiri Reixac 10\u201312 Barcelona 08028 Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nicola","family":"Kielland","sequence":"additional","affiliation":[{"name":"Laboratory of Medicinal Chemistry, Faculty of Pharmacy and Institute of, Biomedicine (IBUB) University of Barcelona  Barcelona Science Park, Baldiri Reixac 10\u201312 Barcelona 08028 Spain"},{"name":"CIBER-BBN, Networking Centre for Bioengineering, Biomaterials &amp; Nanomedicine  Baldiri Reixac 10\u201312 Barcelona 08028 Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Carolina","family":"Estarellas","sequence":"additional","affiliation":[{"name":"Departament de Fisicoqu\u00edmica, Facultat de Farm\u00e0cia, and IBUB Universitat de Barcelona  Prat de la Riba 171 08921 Santa Coloma de Gramenet Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"F. 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