Project

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Project A: The synthesis and studies of new ligands derived from calix[4]pyrroles

Applicant Neier Reinhard
Number 124696
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 01.04.2009 - 31.03.2012
Approved amount 265'835.00
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All Disciplines (2)

Discipline
Organic Chemistry
Inorganic Chemistry

Keywords (11)

Pyrrole; Calix[4]pyrrole; Macrocyclic Ligands; Catalysis; Triphenylene; Extended porphyrins; Discotic mesophases; Calix[4]pyrroles; Macrocylces; Reduction; Metal complexes

Lay Summary (English)

Lead
Lay summary
Lead:In our research we use calix[4]pyrroles as starting materials which are spontaneously formed by a simple chemical process known for more than 120 years. Calix[4]pyrroles are obtained without the need of external instruction. These classes of synthetic transformations have a flavor of spontaneous creation, a phenomenon, which is of general interest. These macrocycles are obtained by a simple process which is very similar to the biosynthetisis of the "pigments of life". They have attracted the attention of scientists interested in biosynthesis, prebiotic synthesis and natural products.Review:In contrast to the natural "pigments of life, the synthetic calix[4]pyrroles do not easily form transition metal complexes. Our group has proposed and developed a strategy, whereby the structurally blocked calix[4]pyrrole pyrroles can be transformed into efficient macrocyclic ligands. The reduction process studied in our group allows to obtain close relatives to the porphyrin-like "pigments of life". The four nitrogen ligands are in geometric positions close to the ones made available by the tetrapyrrolic cofactors. Different diastereomers of our novel ligand syntheticaly feasible and the influence of the relative configuration of the ligand on the metal complexation can be studied. Goal:The goal of our research is to make these novel and unique ligands available by studying new approaches to these ligand, by optimizing the reduction process used so far and by studying the properties of the ligands and their metal complexes.Significance:Our studies enlarge the structural variety of macrocyclices available to the chemists but also to other scientists. Metal complexes of macrocyclic ligands are good candidates for studies in catalysis, in material science, but also as sensors for studies of natural processes. The simplicity of the access studied in our group should make many different ligands available.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
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, 119-122.
Catalytic Epoxidation of Alkenes by the Manganese Complex of a Reduced Porphyrinogen Macrocycle
Bruyneel F, Letondor C, Basturk 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 & CATALYSIS, 354(2-3), 428-440.
Click Chemistry Applied in the Synthesis of Symmetrical Triphenylene-Based Discotic Liquid-Crystalline Dimers
Thevenet D, Neier R (2011), Click Chemistry Applied in the Synthesis of Symmetrical Triphenylene-Based Discotic Liquid-Crystalline Dimers, in SYNTHESIS-STUTTGART, (23), 3801-3806.
Synthesis and characterization of pi-extended porphyrins as potential precursors for the formation of columnar mesophases: Design principles for columnar mesophases need revision?
Herzog B, Neier R (2011), Synthesis and characterization of pi-extended porphyrins as potential precursors for the formation of columnar mesophases: Design principles for columnar mesophases need revision?, in ARKIVOC, 29-44.
SYNTHESES OF RHAZINILAM: A COMPARATIVE REVIEW OF FORTY YEARS OF SYNTHETIC ENDEAVORS
Kholod I, Vallat O, Buciumas AM, Neier R (2011), SYNTHESES OF RHAZINILAM: A COMPARATIVE REVIEW OF FORTY YEARS OF SYNTHETIC ENDEAVORS, in HETEROCYCLES, 82(2), 917-917.
An Efficient Photoinduced Deprotection of Aromatic Acetals and Ketals
Thevenet D, Neier R (2011), An Efficient Photoinduced Deprotection of Aromatic Acetals and Ketals, in HELVETICA CHIMICA ACTA, 94(2), 331-346.
Catalytic Hydrogenation of meso-Octamethylporphyrinogen (Calix[4]pyrrole)
Journot G, Letondor C, Neier R, Stoeckli-Evans H, Savoia D, Gualandi A (2010), Catalytic Hydrogenation of meso-Octamethylporphyrinogen (Calix[4]pyrrole), in CHEMISTRY-A EUROPEAN JOURNAL, 16(14), 4224-4230.
1,4-Bis(hexyloxy)-2,5-diiodobenzene
Thevenet D, Neier R, Sereda O, Neels A, Stoeckli-Evans H (2010), 1,4-Bis(hexyloxy)-2,5-diiodobenzene, in ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 66, 837-2365.
1,4-Bis[4-(tert-butyldiphenylsilyl)buta-1,3-diynyl]benzene
Thevenet D, Neier R, Stoeckli-Evans H (2010), 1,4-Bis[4-(tert-butyldiphenylsilyl)buta-1,3-diynyl]benzene, in ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 66, 839-2378.
2-(2-Naphthyl)-1,3-dioxane
Thevenet D, Neier R, Stoeckli-Evans H (2010), 2-(2-Naphthyl)-1,3-dioxane, in ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 66, 473-3486.
2,2 '-(Propane-2,2-diyl)bis(1H-pyrrole)
Journot G, Neier R, Stoeckli-Evans H (2010), 2,2 '-(Propane-2,2-diyl)bis(1H-pyrrole), in ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 66, 392-2756.
4,4-Bis(1H-pyrrol-2-yl)pentanol
Journot G, Neier R, Stoeckli-Evans H (2010), 4,4-Bis(1H-pyrrol-2-yl)pentanol, in ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 66, 393-2766.
Rac-(2R*,3R*)-S-Ethyl-4-Chloro-3-Hydroxy-2-Phenylbuthanethioate and Rac-(2R*, 3R*)-S-Ethyl-2-Phenyl-3-(tosyloxy) buthanethioate: Dichotomy of the Stereoselectivity of the Mukaiyama Reaction
Vallat O, Buciumas AM, Neier R, Stoeckli-Evans H (2010), Rac-(2R*,3R*)-S-Ethyl-4-Chloro-3-Hydroxy-2-Phenylbuthanethioate and Rac-(2R*, 3R*)-S-Ethyl-2-Phenyl-3-(tosyloxy) buthanethioate: Dichotomy of the Stereoselectivity of the Mukaiyama Reaction, in JOURNAL OF CHEMICAL CRYSTALLOGRAPHY, 40(1), 10-14.

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
CUSO Summer School 2011 Villars 28.08.2011 Villars


Awards

Title Year
Prix Syngenta 2011

Associated projects

Number Title Start Funding scheme
128758 LC-MS Triple Quadrupol Mass Spectrometer for rapid and efficient analysis of chemical and biological samples 01.01.2010 R'EQUIP
112205 Using the lessons from the "pigments of life": Modifications of porphyrinogens and of porphyrins in order to obtain new metal complexes and novel materials 01.04.2006 Project funding (Div. I-III)
140555 The hydrogenation of calix[4]pyrroles leading to the novel ligand system calix[4]pyrrolidine: Their properties and their application 01.04.2012 Project funding (Div. I-III)
112205 Using the lessons from the "pigments of life": Modifications of porphyrinogens and of porphyrins in order to obtain new metal complexes and novel materials 01.04.2006 Project funding (Div. I-III)

Abstract

Project A: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.Project B:Control of the supramolecular organization by optimizing the architecture of single molecules as building blocks constitutes a challenge in device fabrication. The discotic molecules, such as hexaalkoxy-triphenylene, self-organize by p stacking into columnar supramolecular structures facilitating a charge carrier transport along these one dimensional assemblies. The aim of this work is to connect two triphenylenes derivatives with a rigid linker, in order to control the self-organization of the discotic molecules and increase the supramolecular order of the hexagonal columnar mesophase.
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