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The hydrogenation of calix[4]pyrroles leading to the novel ligand system calix[4]pyrrolidine: Their properties and their application

Applicant Neier Reinhard
Number 140555
Funding scheme Project funding (Div. I-III)
Research institution Laboratoire de chimie organique de synthèse Université de Neuchâtel
Institution of higher education University of Neuchatel - NE
Main discipline Organic Chemistry
Start/End 01.04.2012 - 31.12.2015
Approved amount 200'000.00
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All Disciplines (2)

Discipline
Organic Chemistry
Inorganic Chemistry

Keywords (7)

Calix[4]pyrrole; Macrocyclic Ligands; Pyrrole; Stereochemistry; Hydrogenation; Heterogenous; Organocatalysis

Lay Summary (English)

Lead
Lay summary

The hydrogenation of calix[4]pyrroles leading to the novel ligand system calix[4]pyrrolidine: Their properties and their application.

"Let's get practical". With these words George Whitesides and John Deutch are launching an appeal to to rethink the future of chemistry in the 21st century (Nature, 2011, Vol. 469, p. 21-22). To solve the challenges of the 21th century chemistry will have to concentrate on solving problems of importance to our societies.  Our group is concentrating on the bio-inspired approach to novel macrocyclic ligand systems. The prototypical metal complexes of natural macrocycles fullfill vital tasks, such as photochemical energy production, energy storage through redox processes and the transport and use of oxygen. The simple and efficient synthesis of calix[4]pyrrole has been known for more than 125 years. The connectivity of these heterocyclic calix[4]arenes is identical with the skeleton of the "pigments of life". Despite this ressemblence of the connectivity graph, the chemical properties of the porphyrin derived natural "pigments of life" and the synthetic calix[4]pyrroles are completely different. The "pigments of life" are almost ideal ligands and form metal complexes with great ease. The function of the indivudual "pigment of life" depends on the metal but also in a subtle way on the ligand and finally on the second coordination sphere. The goal of our research project is to make use of the efficient access to the calix[4]pyrrole skeleton and to transform these compounds into excellent ligands by a "simple" hydrogenation step. We have reported proof-of-principle results by isolating and characterizing the totally reduced calix[4]pyrrolidine. The great challenge is to make the access to this novel macrocyclic structure efficient and experimentally easy.

Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Corrin Syntheses. Part VI, Corrin Synthesis via A→D Ring Closure. The Construction of A/D-Secocorrin Chromophore Systems by the 'Sulfide Contraction' Method and the Photochemical A/B-Secocorrin→Corrin
Yamada Yasuji, Wehrli Pius, Miljkovic Ducan, Wild Hans-Jakob, Buehler Niklaus, Goetschi Erwin, Golding Bernhard, Loeliger Peter, Gleason John, Pace Brian, Ellis Larry, Hunkeler Walter, Schneider Peter, Fuhrer Walter, Nordmann Rene, Srinivasachar Kasturi, Keese Reinhart, Mueller Klaus, Neier Reinhard, Eschenmoser Albert (2015), Corrin Syntheses. Part VI, Corrin Synthesis via A→D Ring Closure. The Construction of A/D-Secocorrin Chromophore Systems by the 'Sulfide Contraction' Method and the Photochemical A/B-Secocorrin→Corrin, in Helv. Chim. Acta, 98(11-12), 1921-2054.
Real-time protein aggregation monitoring based on a simultaneous light scattering investigation and a Bloch surface wave-based approach
Santi Sara, Barakat Elsie, Neier Reinhard, Herzig Hans Peter (2015), Real-time protein aggregation monitoring based on a simultaneous light scattering investigation and a Bloch surface wave-based approach, in Proceedings of SPIE, 9550(95500V), 1-3.
Synthesis and NMR Spectroscopic Study of the Self-Aggregation of 2-Substituted Benzene-1,3,5-tricarboxyamides
Christian Invernizzi, Claudio Dalvit, Helen Stoeckli-Evans, Reinhard Neier (2015), Synthesis and NMR Spectroscopic Study of the Self-Aggregation of 2-Substituted Benzene-1,3,5-tricarboxyamides, in European Journal of Organic Chemistry, 1015(23), 5115-5127.
A two-catalyst photochemistry route to homochiral rings
Neier Reinhard (2014), A two-catalyst photochemistry route to homochiral rings, in Science, 344(6182), 368-369.
Bloch meets Alzheimer
Herzig Hans Peter, Neier Reinhard, Santi Sara, Barakat Elsie (2014), Bloch meets Alzheimer, in SPG Mitteilungen, 42, 11-14.
Phase-transformation-induced twinning of an iron(III) calix[4]pyrrolidine complex
Journod Guillaume, Neier Reinhard, Stoeckli-Evans Helen (2014), Phase-transformation-induced twinning of an iron(III) calix[4]pyrrolidine complex, in Acta Crystallogr., Sect. C Struct. Chem, 70(7), 644-649.
Preparation of precursors for the synthesis of analogues of rhazinilam
Kholod Inga, Vallat Olivier, Buciumas Ana-Maria, Neier Reinhard (2014), Preparation of precursors for the synthesis of analogues of rhazinilam, in ARKIVOC, (iii), 256-273.
Preparation of precursors for the synthesis of analogues of rhazinilam
Kholod Inga, Vallat Olivier, Buciumas Ana-Maria, Neier Reinhard (2014), Preparation of precursors for the synthesis of analogues of rhazinilam, in ARKIVOC, (3), 256-273.
Professor Pierre Vogel - a tribute
Neier Reinhard, Reymond Jean-Louis (2014), Professor Pierre Vogel - a tribute, in ARKIVOC, (3), 1-5.
Protein-Missfaltungen auf der Spur
Neier Reinhard, Herzig Hans Peter (2014), Protein-Missfaltungen auf der Spur, in Chemiextra, (1-2), 16-17.
Real-time protein aggregation monitoring with a bloch surface wave-based approach
Santi Sara, Barakat Elsie, Descrovi Emiliano, Neier Reinhard, Herzig Hans Peter (2014), Real-time protein aggregation monitoring with a bloch surface wave-based approach, in Proc. SPIE, 9129(912918), 1-9.
Synthetic strategies for the synthesis and transformation of substituted pyrrolines as advanced intermediates for Rhazinilam analogues
Inga Kholod, Olivier Vallat, Ana-Maria Buciumas, Reinhard Neier (2014), Synthetic strategies for the synthesis and transformation of substituted pyrrolines as advanced intermediates for Rhazinilam analogues, in European Journal of Organic Chemistry, 35, 7865-7877.
Real-time Amyloid Aggregation Monitoring with a Photonic Crystal-based Approach
Santi Sara, Musi Valeria, Descrovi Emiliano, Paeder Vincent, Di Francesco Joab, Hvozdara Lubos, van der Wal Peter, Lashuel Hilal A., Pastore Annalisa, Neier Reinhard, Herzig Hans Peter (2013), Real-time Amyloid Aggregation Monitoring with a Photonic Crystal-based Approach, in CHEMPHYSCHEM, 14(15), 3476-3482.
2,2′-[(2S*,6R*)-Piperidine-2,6-diyl]-dipropan-2-ol
Journot G, Neier R, Stoeckli-Evans H (2012), 2,2′-[(2S*,6R*)-Piperidine-2,6-diyl]-dipropan-2-ol, in Acta Crystallographica Section E: Structure Reports Online, 68(3), o857.
2-[2-(Pyrrolidin-2-yl)propan-2-yl]-1H-pyrrole and its amide derivative 1-{2-[2-(1H-pyrrol-2-yl)propan-2-yl]pyrrolidin-1-yl}ethanone
Journot G, Neier R, Stoeckli-Evans H (2012), 2-[2-(Pyrrolidin-2-yl)propan-2-yl]-1H-pyrrole and its amide derivative 1-{2-[2-(1H-pyrrol-2-yl)propan-2-yl]pyrrolidin-1-yl}ethanone, in Acta Crystallographica Section C: Crystal Structure Communications, 68(3), o119-o122.
4-Chloro-benzoyl-meso-octa-methyl-calix[2]pyrrolidino[2]pyrrole: An acyl chloride derivative of a partially reduced calix[4] pyrrole
Journot G, Neier R, Stoeckli-Evans H (2012), 4-Chloro-benzoyl-meso-octa-methyl-calix[2]pyrrolidino[2]pyrrole: An acyl chloride derivative of a partially reduced calix[4] pyrrole, in Acta Crystallographica Section E: Structure Reports Online, 68(4), o976-o977.
Catalytic epoxidation of alkenes by the manganese complex of a reduced porphyrinogen macrocycle
Bruyneel F, Letondor C, Bastürk B, Gualandi A, Pordea A, Stoeckli-Evans H, Neier R (2012), Catalytic epoxidation of alkenes by the manganese complex of a reduced porphyrinogen macrocycle, in Advanced Synthesis and Catalysis, 354(2-3), 428-440.
Synthesis and Reactions of 2-[1-Methyl-1-(pyrrolidin-2-yl)ethyl]-1H-pyrrole and Some Derivatives with Aldehydes: Chiral Structures Combining a Secondary-Amine Group with an 1H-Pyrrole Moiety as Excellent H-Bond Donor
Pordea Anca, Stoeckli-Evans Helen, Dalvit Claudio, Neier Reinhard (2012), Synthesis and Reactions of 2-[1-Methyl-1-(pyrrolidin-2-yl)ethyl]-1H-pyrrole and Some Derivatives with Aldehydes: Chiral Structures Combining a Secondary-Amine Group with an 1H-Pyrrole Moiety as Excellent H-Bond Donor, in HELVETICA CHIMICA ACTA, 95(11), 2249-2264.
Synthesis of α,β- and β,β-linked Dimethoxycarbonyldipyrromethanes by Rothemund-type condensation
Journot G, Stoeckli-Evans H, Neier R (2012), Synthesis of α,β- and β,β-linked Dimethoxycarbonyldipyrromethanes by Rothemund-type condensation, in Synlett, 23(12), 1835-1839.
The hydrogenation of heterocyclic calix[4]arenes, a transformation leading to novel macrocyclic ligands
Journot G, Jones CR, Blangy V, Neier R (2012), The hydrogenation of heterocyclic calix[4]arenes, a transformation leading to novel macrocyclic ligands, in Heterocycles, 85(4), 749-797.

Collaboration

Group / person Country
Types of collaboration
Helen Stoeckli-Evans Switzerland (Europe)
- Publication
Aurora Cruz-Cabeza Great Britain and Northern Ireland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Professor Diego Savoia/ Università di Bologna Italy (Europe)
- Exchange of personnel
Karl Kadish United States of America (North America)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
ParisTech France (Europe)
- in-depth/constructive exchanges on approaches, methods or results

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
6th EuCheMS Conference on Nitrogen Ligands Individual talk Hydrogenation of Calix[4]pyrrole 14.09.2015 Beaune, France Stoeckli-Evans Helen; Maupillier William; Neier Reinhard;
90th Birthday Symposium Professor Sir Alan Battersby Talk given at a conference Cambridge seen as a Postdoc 21.03.2015 Cambridge, Great Britain and Northern Ireland Neier Reinhard;
Chemistry Seminar Innsbruck Individual talk Synthesis of Properties of Partially and Totally Reduced Calix[4]pyrroles 16.10.2014 Innsbruck, Austria Neier Reinhard;
FloHet-2013 Florida Heterocyclic and Synthetic Conference Talk given at a conference Studies of partially reduced Calix[4]pyrroles: Synthesis and Structures 03.03.2013 Gainesville, FL, USA, United States of America Neier Reinhard;
Lecture 3eme Cycle: Science Day Talk given at a conference Hydrogenation of Calixarenes 18.12.2012 Paris, Switzerland Neier Reinhard;
Advanced Education for Master Students in Pharmacy: Quo vadis Medicinal Chemistry Individual talk Natural Products Chemistry and Organic Chemistry: An Essential Interface 03.12.2012 Brno, Czech Republic Neier Reinhard;
Scopus 2012 Awaard Individual talk La chimie en Suisse: Passé et Futur 07.11.2012 Alger, Algeria Neier Reinhard;


Self-organised

Title Date Place
22nd Grasmere Heterocyclic Symposium 07.05.2015 Grasmere, Great Britain and Northern Ireland
21st Grasmere Heterocyclic Symposium 09.05.2013 Grasmere, UK, Great Britain and Northern Ireland
CUSO Science Days 30.07.2012 Basel, Switzerland

Communication with the public

Communication Title Media Place Year
Talks/events/exhibitions Le Feu dans toutes ses couleurs Western Switzerland 2014
Print (books, brochures, leaflets) Contemporary alchemy pages 73-75 International 2013

Associated projects

Number Title Start Funding scheme
124696 Project A: The synthesis and studies of new ligands derived from calix[4]pyrroles 01.04.2009 Project funding (Div. I-III)

Abstract

Calix[4]pyrroles are known for over 100 years. We have been the first to reduce these easy to synthesize macrocylces. The ligand obtained have interesting structures and form metal complexes with transition metals. The synthesis of these reduced forms of calix[4]pyrroles and of analogues of these compounds are studied and their properties will be examined.
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