SUSTAIN: Advancing the Sustainable Nature of Catalysis: New Synthetic Methodologies and Valuable Organic Architectures

Transition metal catalysis has revolutionized the way chemists design and synthesize novel or existing molecules. This has been recently translated into three Nobel Prizes, awarded in 2001, 2005, and 2010. Catalysis is a sustainable process by its nature, as it reduces energy consumption and waste generation. Unfortunately though, most of the transition metal catalysts employed today rely on the use of rare, expensive and often highly-toxic transition metals or the need for stoichiometric oxidants. Sustainable catalysis, an emerging and vibrant concept in Chemistry, offers reliable solutions to these problems by amongst others employing catalysts based on nontoxic or biocompatible and/or abundant, inexpensive metal sources. SUSTAIN will introduce and implement a full set of valuable synthetic chemistry strategies and tools, based on the principles of sustainable chemistry and development. Among others, the project envisages the establishment of groundbreaking highly-efficient technologies of multicomponent, domino, or C-H activation transformations, in some cases done enantioselectively or by utilizing CO2 as chemical feedstock, along with their application in the synthesis of compounds with important biological and technological applications. These transformations are step- and atom-economical, thus inherently green. Moreover, they will result in several breakthroughs, by employing, for the first time in these reactions, sustainable metals such as Cu, Zn, and Mn, or even organocatalysis. SUSTAIN will also develop innovative, highly-efficient Au catalytic systems in underexplored, oxidant-free (and, therefore, significantly more economic and environmentally-benign) cross-coupling reactions, as well as electrocatalytic transformations employing novel, non-noble Co- and Ni-based catalysts. More groundbreaking advancements in the field are anticipated through the targeted Fe- or Mn-catalyzed Csp3-H bond activation tools, or the utilization of new, remote or traceless directing groups for sustainable catalysis in Csp2-H bond activation.

SUSTAIN is being implemented (March 2020 to November 2023) in the Research Group of Prof. Georgios C. Vougioukalakis, at the Department of Chemistry of the National and Kapodistrian University of Athens.

SUSTAIN: Προάγοντας την Αειφορία της Κατάλυσης: Νέες Συνθετικές Μεθοδολογίες και Χρήσιμες Οργανικές Αρχιτεκτονικές

Η κατάλυση που στηρίζεται στα μέταλλα μετάπτωσης έχει φέρει επανάσταση στον τρόπο που οι χημικοί σχεδιάζουν και συνθέτουν νέα ή υπάρχοντα μόρια. Αυτό έχει πρόσφατα μεταφραστεί σε τρία βραβεία Nobel Χημείας, που απονεμήθηκαν τα έτη 2001, 2005 και 2010. Η κατάλυση είναι αειφόρα από τη φύση της, καθώς μειώνει την κατανάλωση ενέργειας και τη δημιουργία αποβλήτων. Δυστυχώς, όμως, οι περισσότεροι σύγχρονοι καταλύτες στηρίζονται σε σπάνια, κοστοβόρα και συχνά τοξικά μέταλλα μετάπτωσης ή στη στοιχειομετρική χρήση οξειδωτικών. Η αειφόρος κατάλυση, ένας δυναμικός τομέας αιχμής στη Χημεία, παρέχει αξιόπιστες λύσεις σε αυτά τα προβλήματα, μεταξύ άλλων χρησιμοποιώντας καταλύτες που στηρίζονται σε μη τοξικά ή βιοσυμβατά ή/και άφθονα, χαμηλού κόστους μέταλλα. Το έργο SUSTAIN θα εισάγει και θα αναπτύξει ένα ολοκληρωμένο σύνολο πρωτοποριακών συνθετικών στρατηγικών και εργαλείων, στηριζόμενο στις αρχές της βιώσιμης χημείας και ανάπτυξης. Μεταξύ άλλων, θα αναπτυχθούν καινοτόμες, αποδοτικές τεχνολογίες χημικών μετασχηματισμών πολλών συστατικών, αντιδράσεων καταρράκτη ή αντιδράσεων ενεργοποίησης δεσμών C-H, σε ορισμένες περιπτώσεις εναντιοεκλεκτικά ή χρησιμοποιώντας το CO2 ως πρώτη ύλη, σε συνδυασμό με την εφαρμογή τους στη σύνθεση ενώσεων με σημαντικές βιολογικές και τεχνολογικές εφαρμογές. Αυτοί οι μετασχηματισμοί χαρακτηρίζονται από οικονομία σταδίων και ατόμων, οπότε είναι εγγενώς «πράσινοι». Επιπλέον, θα έχουν σημαντική απήχηση σε διεθνές επίπεδο, χρησιμοποιώντας, για πρώτη φορά σε αυτές τις αντιδράσεις, αειφόρα μέταλλα όπως ο Cu, ο Zn και το Mn ή οργανοκαταλύτες. Θα αναπτυχθούν επίσης πρωτότυπα, εξαιρετικά χρήσιμα καταλυτικά συστήματα Au υψηλής απόδοσης, για τις ελάχιστα μελετημένες αντιδράσεις σύζευξης απουσία οξειδωτικού (οι οποίες είναι οικονομικές και φιλικές προς το περιβάλλον), καθώς και ηλεκτροκαταλυτικοί μετασχηματισμοί στηριζόμενοι στα μη σπάνια μέταλλα Co και Ni. Πρωτοποριακές ανακαλύψεις αναμένονται επίσης μέσω των αντιδράσεων ενεργοποίησης δεσμών Csp3-H από καταλυτικά συστήματα Fe και Mn ή μέσω της χρήσης νέων κατευθυντήριων ομάδων, που είναι απομεμακρυσμένες ή δεν αφήνουν ίχνη, στην αειφόρα κατάλυση για ενεργοποίηση δεσμών Csp2-H.

Organization and Workflow of SUSTAIN

SUSTAIN’s Publications in Peer-Reviewed International Journals

  • Neofotistos, S. P.; Tzouras, N. V.; Pauze, M.; Gomez-Bengoa, E.; Vougioukalakis, G. C.* Adv. Synth. Catal. 2020, 362, 3872-3885. "Manganese-Catalyzed Multicomponent Synthesis of Tetrasubstituted Propargylamines: System Development and Theoretical Study"
  • Zorba, L. P.; Vougioukalakis, G. C.* Coord. Chem. Rev. 2021, 429, 213603. "The Ketone-Amine-Alkyne (KA2) Coupling Reaction: Transition Metal-Catalyzed Synthesis of Quaternary Propargylamines"
  • Tonis, E.; Stein, F.; Stamatopoulos, I. K.; Stubbe, J.; Zarkadoulas, A.; Sarkar, B.;* Vougioukalakis, G. C.* Synlett 2021, 32, 616-620. "A Pd-free Sonogashira Coupling Protocol Employing an In-Situ-Prepared Copper/Chelating 1,2,3-Triazolylidene System"
  • Zorba, L. P.; Egana, E.; Gomez-Bengoa, E.; Vougioukalakis, G. C.* ACS Omega 2021, 6, 23329-23346. "Zinc Iodide Catalyzed Synthesis of Trisubstituted Allenes from Terminal Alkynes and Ketones"
  • Tzouras, N. V.; Scattolin, T.; Gobbo, A.; Bhandary, S.; Rizzolio, F.;* Cavarzerani, E.; Canzonieri, V.; Van Hecke, K.; Vougioukalakis, G. C.; Cazin, C. S. J.; Nolan, S. P.* ChemMedChem 2022, e202200135. "A Green Synthesis of Carbene-Metal-Amides (CMAs) and Carboline-Derived CMAs with Potent in vitro and ex vivo Anticancer Activity"
  • Tzouras, N. V.; Gobbo, A.; Pozsoni, N. B.; Chalkidis, S. G.; Bhandary, S.; Van Hecke, K.; Vougioukalakis, G. C.;* Nolan, S. P.* Chem. Commun. 2022, 58, 8516-8519. "Hydrogen bonding-enabled gold catalysis: ligand effects in gold-catalyzed cycloisomerizations in hexafluoroisopropanol (HFIP)"

SUSTAIN’s Invited Talks and Presentations in International and National Conferences

  • Vougioukalakis, G. C. "Creating Complexity via Sustainable Catalytic Transformations: Multicomponent Reactions, Cross-Couplings, and CO2 Monetization" University of Crete, Department of Chemistry, Greece – Invited Online Talk (December 11, 2020)
  • Vougioukalakis, G. C. "Sustainable Catalysis in Useful Organic Transformations: Multicomponent Reactions, Cross-Couplings, and CO2 Activation" Athens Conference on Advances in Chemistry 2020, Online conference due to the COVID-19 outbreak (March 2021 - Oral Presentation)
  • Zorba, L. P.; Vougioukalakis, G. C. "Zinc Iodide Catalyzed Allenylation of Terminal Alkynes towards Trisubstituted Allenes under Conventional or Microwave Irradiation Conditions" Athens Conference on Advances in Chemistry 2020, Online conference due to the COVID-19 outbreak (March 2021 - Oral Presentation)
  • Kaplanai, E.; Tonis, E.; Zagranyarski, Y.; Vougioukalakis, G. C. "A novel, domino O-H/C-H activation reaction towards the synthesis of oxygen-doped polyaromatic molecules with technological applications" Athens Conference on Advances in Chemistry 2020, Online conference due to the COVID-19 outbreak (March 2021 - Oral Presentation)
  • Chalkidis, S. G.; Vougioukalakis, G. C. "A novel, copper(I)-NHC well-defined catalytic system for the multicomponent synthesis of quaternary propargylamines" Athens Conference on Advances in Chemistry 2020, Online conference due to the COVID-19 outbreak (March 2021 - Oral Presentation)
  • Tonis, E.; Stein, F.; Stamatopoulos, I. K.; Stubbe, J.; Zarkadoulas, A.; Sarkar, B.; Vougioukalakis, G. C. "A Pd-Free Sonogashira Coupling Protocol Employing an In-Situ-Prepared Copper/Chelating 1,2,3-Triazolylidene System" Athens Conference on Advances in Chemistry 2020, Online conference due to the COVID-19 outbreak (March 2021 - Oral Presentation)
  • Tonis, E.; Vougioukalakis, G. C. "A Straightforward Protocol for the Synthesis of 4-Alkylidene-2-Thione-1,3-Oxathiolanes" Athens Conference on Advances in Chemistry 2022, Athens, Greece (June-July 2022 - Poster Presentation)
  • Chalkidis, S. G.; Vougioukalakis, G. C. "Straightforward Synthesis of 4,4-Disubstituted-1,3-Thiazolidine-2-Thiones from Quaternary Propargylamines and Carbon Disulfide" Athens Conference on Advances in Chemistry 2022, Athens, Greece (June-July 2022 - Poster Presentation)
  • Mai, M.; Rotas, G.; Sarkar, B.; Vougioukalakis, G. C. "Synthesis and Characterization of a New Family of Fullerene Derivatives" Athens Conference on Advances in Chemistry 2022, Athens, Greece (June-July 2022 - Poster Presentation)
  • Zorba, L. P.; Vougioukalakis, G. C. "One pot synthesis of thiazolidin-2-ylideneamines" Athens Conference on Advances in Chemistry 2022, Athens, Greece (June-July 2022 - Oral Presentation)
  • Kaplanai, E.; Tonis, E.; Drymona, M.; Zagranyarski, Y.; Vougioukalakis, G. C. "A new, domino O-H/C-H activation reaction towards the synthesis of oxygen-doped polyaromatic molecules with potential technological and biological applications" Athens Conference on Advances in Chemistry 2022, Athens, Greece (June-July 2022 - Oral Presentation)
  • Danopoulou, M. A.; Zorba, L.; Cobelic, B.; Turel, I.; Vougioukalakis, G. C. "Catalytic Activity Evaluation of Zn(II)-Hydrazone Complexes in the KA2 Coupling Reaction" Athens Conference on Advances in Chemistry 2022, Athens, Greece (June-July 2022 - Poster Presentation)
  • Giannopoulos, D.; Zorba, L.; Zisis, C.; Pitsikalis, M.; Vougioukalakis, G. C. "Development of a novel, step-growth polymerization strategy, based on a multi-component coupling reaction" Athens Conference on Advances in Chemistry 2022, Athens, Greece (June-July 2022 - Oral Presentation)
  • Drymona, M.; Kaplanai, E.; Georganakis, D.; Vougioukalakis, G. C. "Towards sustainable homoallylic alcohols isomerization/oxidation with applications in fine chemicals industry" Athens Conference on Advances in Chemistry 2022, Athens, Greece (June-July 2022 - Poster Presentation)
  • Kaplanai, E.; Tonis, E.; Drymona, M.; Zagranyarski, Y.; Vougioukalakis, G. C. "Α DOMINO O-H/C-H ACTIVATION TRANSFORMATION TOWARDS THE SYNTHESIS OF OXYGEN-DOPED POLYCYCLIC AROMATIC MOLECULES" 17th Belgian Organic Synthesis Symposium, Namur, Belgium (July 2022 - Poster Presentation)
  • Zorba, L. P.; Vougioukalakis, G. C. "KA2-based, one pot synthesis of thiazolidin-2-ylideneamines" 17th Belgian Organic Synthesis Symposium, Namur, Belgium (July 2022 - Poster Presentation)

Dissemination to the Public in the Framework of SUSTAIN

  • SUSTAIN participated in "European Researchers' Night 2021" with a 3-minute video (September 24, 2021). The video can be accessed here: http://users.uoa.gr/~vougiouk/Downloads/Researchers%20Night%202021.mp4
  • SUSTAIN organized an on-line, open to the public dissemination event with talks from Professors Nolan (Ghent University), Ribas (Girona University), and Sarkar (Stuttgardt University), as well as from the Vougioukalakis Group members (July 4, 2022).
  • SUSTAIN organized a Project-Open day, during which many interested people visited the Vougioukalakis Labs and got informed about the SUSTAIN project (July 4, 2022).

SUSTAIN’s External Collaborators (not funded)

Contact

Email

vougiouk@chem.uoa.gr