laboratoire de Réactivité et Catalyse Organique (RCO)

laboratoire de Réactivité et Catalyse Organique (RCO)

Presentation

Laboratory of Reactivity and Organic Catalysis (RCO, Professor Guillaume Berionni)


Our group's research interests range over a variety of topics within the fields of organometallic, main-group and physical organic chemistry.
Our current research focuses on the development of structurally unique nitrogen- and phosphorus containing Lewis bases and new carbon- and boron-containing Lewis acids.
We investigate their reactivity and properties, and then combine them in pairs for creating new bifunctional acid–base catalysts. Creating new chemical entities based on main-group elements to mimic the rich and multifaceted chemistry of transition-metal complexes is an exciting challenge and requires a combination of state-of-the-art synthetic and computational chemistry.
The reactivities of these metallomimetic molecular systems are investigated quantitatively by kinetics and thermodynamic measurements which allows the subsequent fine-tuning and optimization of their structures and their efficient implementations in new chemical processes (hydrogenation reactions, CH borylation reactions, small molecules activation).
The development of ground-breaking main-group catalysts based on the most abundant elements in the earth crust will have a wide impact on chemical energy transformation and storage, as well as on bulk and fine chemical synthesis.

 

Funding Agencies

 

The group is funded since 2018 by the Belgian National Fund for Scientific Research (Fonds National de la Recherche Scientifique FNRS)

Since 2022 the group is funded by the European Research Council (ERC) under the Horizon Europe research and innovation programme

Within the context of an ARC inter-university collaboration with the UCLouvain University, the group is supported by the Fédération Wallonie-Bruxelles funds for fundamental research, through its ‘Actions de Recherche Concertées’ (ARC, Collective Research Initiatives) programme.


Prof. Guillaume Berionni (Namur Institute of Structured Matter - University of Namur) has been recently awarded an ERC consolidator grant.
With this funding instrument, the European Research Council enables outstanding scientists to implement pioneering concepts over a period of five years and thus strengthens the European research landscape.
The ERC received 2652 consolidator grant proposals, and a total of 313 laureates were funded in Europa. In the physical sciences and engineering PE5 panel (Synthetic Chemistry and Materials), a total of 12 ERC CoG grants were awarded this year in Europa, among which only one (this project B-YOND) was awarded in Belgium. ERC Consolidator Grants are designed to support excellent research programs which must demonstrate ground-breaking nature and multidisciplinary ambition.


Inspired by transition-metal catalysis and main-group chemistry, the recently funded ERC project “B-yond” aims at reprograming molecular systems based on s and p block elements to overstep current chemistry reactivity rules.
A milestone of this project is the formulation of acids and bases with minimal reorganization energies suitable for promoting new catalytic processes. The development of ground-breaking main-group catalysts based on the most abundant elements in the earth crust will have a wide impact on chemical materials transformation, as well as on bulk and fine chemical synthesis.

The research outcomes will lay the basis for developing new energy and resources management strategies, notably through novel approaches to catalysts design and sustainable materials development, by avoiding the use of precious transition-metal elements.
Thus, the research project B-YOND addresses important challenges in the quest for a sustainable future, since Berionni and his working group will develop new reactive species and catalysts that benefit a variety of chemical technologies.

Additional links:


Publications

 

54

54

 

 

Regioselective Transition-Metal Free Arenes C-H Borylations: From Directing Groups to Borylation Template Reagents, G. Berionni, Angew. Chem. Int. Ed. 2022, accepted (highlight).

 [Download]

 

 

 

 

53Publi 53

 

 

Reprogramming Main-Group Compounds: Toward New Superelectrophilic and Superacidic Catalysts, G. Berionni, Chimie Nouvelle, 2022, 139, 27-29.

DOI: 10.52809/cn2022.nxmn2068

[download]



 

52

Publication 53

A Selenium Substituted Pyramidal 9-Boratriptycene Lewis Acid, A. Osi, N. Tumanov, J. Wouters, A. Chardon, G. Berionni, Synthesis 2022, online, DOI: 10.1055/a-1840-5680.

 [download]

 

 

51


 

9-phosphatriptycene derivatives: from their weak basicity to their application in frustrated Lewis pair chemistry

D. Mahaut, G. Berionni, B. Champagne, J. Phys. Chem. A 2022, 126, 18, 2794–2801

[download]



50

publication 51


 

 

Frustrated Lewis pair-catalyzed hydrogenation of unactivated alkenes with sterically hindered 9-phosphatriptycenes

D. Mahaut, B. Champagne, G. Berionni, 2022, ChemCatChem 2022,14,   e202200294.

[download]





49

Pub 49

Taming the Lewis Superacidity of Non-Planar Boranes: C-H Bond Activation and Non-Classical Binding Modes at Boron

A. Osi, D. Mahaut, N. Tumanov, L. Fusaro, J. Wouters, B. Champagne, A. Chardon, G. Berionni. Angew. Chem. Int. Ed. 2022, 61, e202112342.

 [download]

48

Publi 48

Young Career Focus presents Guillaume Berionni, Synform, 2021, 159-161

[download]







47

Publi 47



Future Prospects in Boron Chemistry: Boron Lewis Acids in Perspective

Chem. Syn. 2021, 1:10.

DOI: 10.20517/cs.2021.11


[download]

 

 

 

46

Dam pub


Rational Development of a Metal-Free Bifunctional System for the C-H Activation of Methane: A Density Functional Theory Investigation

D. Mahaut, A. Chardon, L. Mineur, G. Berionni, B. Champagne, ChemPhysChem 2021, 22, 1958–1966.

[download]




 45

 


Six-membered Rings with One Phosphorus Atom

F. Rammal, V. Magné, G. Berionni, S. Lakhdar, Comprehensive Heterocyclic Chemistry IV, Elsevier, 2022, Volume 7, 685-717 (book chapter).


[download]

44




Four-membered Rings with One Phosphorus, Arsenic, Antimony, or Bismuth Atom

V. Magné, F. Rammal, G. Berionni, S. Lakhdar, Comprehensive Heterocyclic Chemistry IV, Elsevier, 2022, Volume 2, 335-362 (book chapter).


 [download]





 

43

Lei dalton

Sterically hindered ortho-substituted phosphatriptycenes as configurationally stable P-chirogenic triarylphosphines

L. Hu, D. Mahaut, N. Tumanov, J. Wouters, L. Collard, R. Robiette, G. Berionni, Dalton Trans. 2021, 50, 4772-4777

[download]

42

Pub Math

Triptycene Boronates, Boranes, and Boron Ate‐Complexes: Toward Sterically Hindered Triarylboranes and Trifluoroborates

M. Gama, X. Antognini Silva, T-H. Doan, A. Osi, A. Chardon, N. Tumanov, J. Wouters, G. Berionni, Eur. J. Org. Chem. 2021, 1440–1445

[download]

41

pub 41

Methylene Bridging Effect on the Structures, Lewis Acidities and Optical Properties of Semi Planar Triarylboranes

T.-H. Doan, A. Chardon, A. Osi, D. Mahaut, N. Tumanov, J. Wouters, B. Champagne, G. Berionni, Chem. Eur. J. 2021, 27, 1736-1743.

[download]

40Syn

Non-planar Boron Lewis Acids Taking the Next Step: Development of Tunable Lewis Acids, Lewis Superacids and Bifunctional Catalysts

A. Chardon, A. Osi, D. Mahaut, A. Ben Saida, G Berionni, Synlett. 2020, 31, 1639-1648.

[download]

39

Bora

Controlled Generation of 9-Boratriptycene by Lewis Adduct Dissociation: Accessing a Unique Non-Planar Triarylborane

A. Chardon, A. Osi, D. Mahaut, T.-H. Doan, N. Tumanov, J. Wouters, L. Fusaro, B. Champagne, G Berionni, Angew. Chem. Int. Ed. 2020, 59, 12402-12406.

[download]

38

Pushing the Lewis Acidity Boundaries of Boron Compounds With Non-Planar Triarylboranes Derived from Triptycenes

A. Ben Saida, A. Chardon, A. Osi, N. Tumanov, J. Wouters, A. I. Adjieufack, B. Champagne, G. Berionni,  Angew. Chem. Int. Ed. 2019, 58, 16889–16893.

[download]

 

37

Complementary Synthetic Approaches toward 9-Phosphatriptycene and Structure–Reactivity Investigations of Its Association with Sterically Hindered Lewis Acids

L. Hu, D. Mahaut, N. Tumanov, J. Wouters, R. Robiette, G. Berionni, J. Org. Chem. 2019, 84, 1126811274.

[download]

 

36

 


The Halogen–Samarium Exchange Reaction: Synthetic Applications and Kinetics

L. Anthore‐Dalion, A. D. Benischke, B. Wei, G Berionni, P. Knochel, Angew. Chem. Int. Ed. 2019, 58, 4046.

[download]

 

35

 

Opening Up New Research Lines in Lewis Acid/Base Catalysis

G. Berionni, L. Hu, A. Ben Saida, A. Chardon, M. Gama, A. Osi, D. Mahaut, X. Antognini Silva, Chimie Nouvelle, 2018, 128, 13.

[download]

 

34 organolanthanum

Stereospecific Allylic Functionalization: The Reactions of Allylboronate Complexes with Electrophiles
A. D. Benischke, L. Anthore-Dalion, G. Berionni, P. Knochel, Angew. Chem. Int. Ed. 2017, 51, 16390-16394.
[download]

 

33 allylation Stereospecific Allylic Functionalization: The Reactions of Allylboronate Complexes with Electrophiles
C. García-Ruiz, J. L.-Y. Chen, C. Sandford, K. Feeney, G. Berionni, H. Mayr, V. K. Aggarwal, J. Am. Chem. Soc., 2017, 139, 15324-15327.
[download]
32 borylation

Mechanistic studies of formal thioboration reactions of alkynes
A. Issaian, D. J. Faizi, J. O. Bailey, P. Mayer, G. Berionni*, D. A. Singleton*, S. A. Blum*, J. Org. Chem. 2017, 82, 8165-8178.
[download]

31 lithiathion Barbier continuous flow preparation and reactions of carbamoyllithiums for nucleophilic amidation
M. A. Ganiek, M. R. Becker, G. Berionni, H. Zipse, P. Knochel*, Chem. Eur. J. 2017, 23, 10280-10284.
[download]
30 i_z0304 Nucleophilicities and Lewis basicities of sterically hindered pyridines
E. Follet, H. Zipse, S. Lakhdar, A. R. Ofial, G. Berionni*, Synthesis 2017, 49, 3495-3504. [special issue on the occasion of the 70th birthday of Professor Herbert Mayr]
[download]
29 superelectophile Superelectrophilicity in Michael-Type Reactions: Water Addition to 4-Nitrobenzodifuroxan
S. Lakhdar,* G. Berionni*, F. Terrier,* Synthesis 2017, 49, 3453-3459. [special issue on the occasion of the 70th birthday of Professor Herbert Mayr]
[download]
28 chem_toc Reactivity-tuning in frustrated Lewis pairs: nucleophilicities and lewis basicities of sterically hindered phosphines
E. Follet, P. Mayer, D. S. Stephenson, A. R. Ofial, G. Berionni*, Chem. Eur. J. 2017, 23, 7422-7427.
[download]
27 fluorenyliums Structures, Lewis acidities, electrophilicities, and protecting group abilities of phenyl-fluorenylium and tritylium ions.
E. Follet, P. Mayer, G. Berionni*, Chem. Eur. J. 2017, 23, 623-630.
[download][Selected as hot paper]
26 zirconocenes Nucleophilicity of alkyl zirconocene and titanocene precatalysts and kinetics of activation by carbenium ions and by B(C6F5)3.
G. Berionni*, H. Kurouchi, L. Eisenburger, H. Mayr, Chem. Eur. J. 2016, 22, 11196-11200.
[download]
25 frustrated_lewis Scope and mechanisms of frustrated Lewis pair catalyzed hydrogenation reactions of electron-deficient C=C double bonds
V. Morozova, P. Mayer, G. Berionni*, Angew. Chem. Int. Ed. 2015, 54, 14508-14512.
[download]

24

indolylmethylium

Structure and Reactivity of Indolyl-methylium Ions: Scope and Limitations in Synthetic Applications
E. Follet, G. Berionni, P. Mayer, H. Mayr, J. Org. Chem. 2015, 80, 8643-8656.
[download]
23 alkyl_ate_complexes Structure and Reactivity of Boron-Ate Complexes Derived from Primary and Secondary Boronic Esters
K. Feeney, G. Berionni, H. Mayr, V. K. Aggarwal, Org. Lett. 2015, 17, 2614-2617.
[download]
22 boron_ate_complexes Fine-Tuning of the Nucleophilic Reactivities of Boron-Ate Complexes Derived From Aryl and Heteroaryl Boronic Esters
G. Berionni, A. I. Leonov, P. Mayer, A. R. Ofial, H. Mayr, Angew. Chem. Int. Ed. 2015, 54, 2780-2783.
[download]
21 secondary_alkylithium Stereoselective Synthesis and Reactions of Secondary Alkyllithium Reagents Functionalized at the 3-Position
K. Moriya, D. Didier, M. Simon, J. M. Hammann, G. Berionni, K. Karaghiosoff, H. Zipse, H. Mayr, P. Knochel, Angew. Chem. Int. Ed. 2015, 54, 2754-2757.
[download]
20 aromatic_radialenes Aromaticity evaluations of planar [6]radialenes
Guillaume Berionni*, Judy I. Chia Wu, Paul v R. Schleyer, Org. Lett. 2014, 16, 6116-6119
[download]
19 hydride_donors Di- and Triarylmethylium Ions as Probes for the Ambident Reactivities of Carbanions Derived from 5-Benzylated Meldrum's Acid
X. Chen, Y. Tan, G. Berionni, A. R. Ofial, H. Mayr, Chem. Eur. J. 2014, 20, 11069-11077.
[download]
18 tmpbases New In Situ Trapping Metalations of Functionalized Arenes and Heteroarenes with TMPLi in the Presence of ZnCl2 and Other Metal Salts
A. Frischmuth, M. Fernández, N. M. Barl, F. Achrainer, H. Zipse, G. Berionni, H. Mayr, K. Karaghiosoff, P. Knochel, Angew. Chem. Int. Ed. 2014, 53, 7928-7932.
[download]
17 electrophilicity Mechanistic studies and quantification of the electrophilicity of aromatic triflones in sigma-complexation and SNAr reactions
N. El Guesmi, G. Berionni, B.H Asghar, J. Fluorine. Chem. 2014, 160, 41-47
[download]
16 diastereoselectives

Diastereoselective Synthesis of Open-Chain Secondary Alkyllithium Compounds and Trapping Reactions with Electrophiles
G Dagousset, K Moriya, R Mose, G Berionni, K Karaghiosoff, P Knochel, Angew. Chem. Int. Ed. 2014, 53, 1425-1429.
[download]

 

15 aromatic_substitution Electronic and solvent effects on kinetics of SNAr substitution reactions of substituted anilines with 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole
N. El Guesmi, G. Berionni, B.H Asghar, Monatsh. Chemie (Chemical Monthly) 2013, 144, 1537-1545.
[download]
14 trifluorobates Electrophilic Aromatic Substitutions of Aryltrifluoroborates with Retention of the BF3- Group: Quantification of the Activating and Directing Effects of the Trifluoroborate Group
G. Berionni, V. Morozova, M. Heininger, P. Mayer, P. Knochel, H. Mayr, J. Am. Chem. Soc. 2013, 135, 6317-6324.
[download][Highlighted in Synfact, 2013, 9, 723]
13 nucleophilicity_scales Nucleophilicity parameters for designing transition metal-free C-C bond forming reactions of organoboron compounds
G. Berionni, B. Maji, P. Knochel, H. Mayr, Chem. Sci. 2012, 3, 878-882.
[download][Highlighted in the blog of the RSC]
12 super_dmap_organocatalysts Synthesis and Reactivity of Highly Nucleophilic Pyridines
N. De Rycke, G. Berionni, F. Couty, H. Mayr, R. Goumont, O. R. P. David, Org. Lett. 2011, 13, 530-533.
[download][Highly cited paper]
11 tetrazolopyridines The N-Alkylation of Substituted 4-Tetrazolo[1, 5-a]pyridines: Easy Access to a New Series of Electrophiles
G. Berionni, M. Branca, B. Pégot, J. Marrot, E. Kizilian, R. Goumont, Eur. J. Org. Chem. 2011, 26, 5104-5113.
[download]


Publications 1-10 (Master and PhD work)



[See my Google Scholar profile]



Open Positions

Projects are currently available in the areas of organoboron chemistry (development of novel Lewis acids, catalysts, receptors), organic reactivity and catalysis (reactivities of frustrated Lewis pairs) and of organometallic chemistry.

If you are interested in pursuing research in any of the areas mentioned above, and would like to discuss the available projects and positions in 2022-2022, please contact Professor Guillaume Berionni by e-mail.

 

Professor Guillaume Berionni

 

Team Pictures

 

Equipment

 

 Laboratoire de Réactivité et Catalyse Organique (RCO, Professeur Guillaume Berionni)