Anamarija Bris
@irb.hr
Division of Organic Chemistry and Biochemistry
Ruđer Bošković Institute
Scopus Publications
Scopus Publications
Anamarija Briš, Mathieu G. Baltussen, Guilherme L. Tripodi, Wilhelm T. S. Huck, Pietro Franceschi, and Jana Roithová
Wiley
AbstractComplex reaction mixtures, like those postulated on early Earth, present an analytical challenge because of the number of components, their similarity, and vastly different concentrations. Interpreting the reaction networks is typically based on simplified or partial data, limiting our insight. We present a new approach based on online monitoring of reaction mixtures formed by the formose reaction by ion‐mobility‐separation mass‐spectrometry. Monitoring the reaction mixtures led to large data sets that we analyzed by non‐negative matrix factorization, thereby identifying ion‐signal groups capturing the time evolution of the network. The groups comprised ≈300 major ion signals corresponding to sugar‐calcium complexes formed during the formose reaction. Multivariate analysis of the kinetic profiles of these complexes provided an overview of the interconnected kinetic processes in the solution, highlighting different pathways for sugar growth and the effects of different initiators on the initial kinetics. Reconstructing the network's topology further, we revealed so far unnoticed fast retro‐aldol reaction of ketoses, which significantly affects the initial reaction dynamics. We also detected the onset of sugar‐backbone branching for C6 sugars and cyclization reactions starting for C5 sugars. This top‐down analytical approach opens a new way to analyze complex dynamic mixtures online with unprecedented coverage and time resolution.
Anamarija Briš and Davor Margetić
MDPI AG
Great efforts of the scientific community are focused on the development of catalysts for the reduction of carbon dioxide (CO2) to useful molecules such as carbon monoxide, formic acid, methanol, ethanol, methane, ethylene, or acetate. Various metal porphyrin complexes were synthesized and studied to develop highly active and selective catalysts. While the substituents on the porphyrin core (the primary coordination sphere) determine the reactivity of the metal, the introduction of the secondary coordination is important for the binding and activation of CO2. In this review, selected examples of iron porphyrin catalysts with a secondary coordination sphere capable of stabilizing intermediates of the CO2 reduction process by hydrogen bonding are presented.
Anamarija Briš, Yasujiro Murata, Yoshifumi Hashikawa, and Davor Margetić
Elsevier BV
Petar Štrbac, Anamarija Briš, and Davor Margetić
MDPI AG
Synthesis of N,N′-Di-Boc-2H-isoindole-2-carboxamidine, the first representative of isoindoles containing guanidine functionality, was carried out. The cycloaddition reactivity of this new Diels–Alder heterodiene was studied and the title compound was employed as a cycloaddition delivery reagent for guanidine functionality. Higher reactivity was found in comparison with the corresponding pyrrole derivative. Substitution with fluorine or guanidine functionality does not change the reactivities of isoindoles, and these findings are in good accord with computational results.
Roelant Hilgers, Sin Yong Teng, Anamarija Briš, Aleksandr Y. Pereverzev, Paul White, Jeroen J. Jansen, and Jana Roithová
Wiley
Enantioselective reactions are at the core of chemical synthesis. Their development mostly relies on prior knowledge, laborious product analysis and post-rationalization by theoretical methods. Here, we introduce a simple and fast method to determine enantioselectivities based on mass spectrometry. The method is based on ion mobility separation of diastereomeric intermediates, formed from a chiral catalyst and prochiral reactants, and delayed reactant labeling experiments to link the mass spectra with the reaction kinetics in solution. The data provide rate constants along the reaction paths for the individual diastereomeric intermediates, revealing the origins of enantioselectivity. Using the derived kinetics, the enantioselectivity of the overall reaction can be predicted. Hence, this method can offer a rapid discovery and optimization of enantioselective reactions in the future. We illustrate the method for the addition of cyclopentadiene (CP) to an α,β-unsaturated aldehyde catalyzed by a diarylprolinol silyl ether.
Anamarija Briš, Zoran Glasovac, and Davor Margetić
Royal Society of Chemistry (RSC)
Density functional theory calculations (B3LYP) were employed in the study of gas-phase basicity (GB) and pKa of three different types of cyclic guanidines differing in the number of nitrogen atoms incorporated in rings.
Mateja Đud, Anamarija Briš, Iva Jušinski, Davor Gracin, and Davor Margetić
Beilstein Institut
Friedel–Crafts (FC) acylation reactions were exploited in the preparation of ketone-functionalized aromatics. Environmentally more friendly, solvent-free mechanochemical reaction conditions of this industrially important reaction were developed. Reaction parameters such as FC catalyst, time, ratio of reagents and milling support were studied to establish the optimal reaction conditions. The scope of the reaction was explored by employment of different aromatic hydrocarbons in conjunction with anhydrides and acylation reagents. It was shown that certain FC-reactive aromatics could be effectively functionalized by FC acylations carried out under ball-milling conditions without the presence of a solvent. The reaction mechanism was studied by in situ Raman and ex situ IR spectroscopy.
Anamarija Briš, Juraj Jašík, Iztok Turel, and Jana Roithová
Royal Society of Chemistry (RSC)
ESI-MS study of ruthenium complexes shows their high selectivity toward thiol containing molecules and formation of larger thiolate-bound clusters in absence of a protecting ligand such as pta.
Anamarija Briš, I. Turel and J. Roithová
Lorena Capdevila, Erik Andris, Anamarija Briš, Màrius Tarrés, Steven Roldán-Gómez, Jana Roithová, and Xavi Ribas
American Chemical Society (ACS)
Cross-coupling transformations are a powerful tool in organic synthesis. It is known that this kind of transformation undergoes 2-electron redox processes, and, for this reason, silver has been nearly forgotten as catalyst for cross-couplings because silver is mainly considered as a 1-electron redox metal. Herein, we disclose effective Ag(I)-catalyzed cross-coupling transformations using bidentate aminoquinoline as a directing group toward different nucleophiles to form C–C, C–N, and C–O bonds. DFT calculations indicate the feasible oxidative addition of L1-I substrate via the Ag(I)/Ag(III) catalytic cycle. Furthermore, ion spectroscopy experiments suggest a highly reactive aryl-Ag(III) that in the absence of nucleophiles reacts to form an intermolecular cyclic product [5d-Ag(I)-CH3CN], which in solution forms 5a. This work proves that silver can undergo 2-electron redox processes in cross-coupling reactions like Pd and Cu.
Anamarija Briš, Mateja Đud and D. Margetić
The mechanochemical N-alkylation of imide derivatives was studied. Reactions under solvent-free conditions in a ball mill gave good yields and could be put in place of the classical solution conditions. The method is general and can be applied to various imides and alkyl halides. Phthalimides prepared under ball milling conditions were used in a mechanochemical Gabriel synthesis of amines by their reaction with 1,2-diaminoethane.
Anamarija Briš, Pavle Trošelj, and Davor Margetić
Croatian Chemical Society
Complexations of bis(Zn(II)porphyrin) receptor possessing moderately flexible linkers with aliphatic α,ω-diamines was studied by UVvis and NMR spectroscopy. The strongest binding was identified for 1,8-diaminooctane, with the binding constant by one order of the magnitude larger than the next diamine homologue 1,7-diaminoheptane.
Anamarija Briš, Pavle Trošelj, Davor Margetić, Lucia Flamigni, and Barbara Ventura
Wiley
Self-assembled bis(zinc porphyrin)-bispyridinopyrrolidinofullerene coordination complexes were obtained in solution. Two [5]polynorbornane-bridged bis-porphyrins were used that differed in the arms containing porphyrin units: whereas 1 has rigid [5]polynorbornane linkers, compound 2 has additional flexible propyl chains. The different geometries of the two hosts affect both the complexation process and the photoreactivity of the final product. Formation of the complexes, characterized by absorption, emission, and NMR spectroscopy, occurs with association constants in the order of 104 and 106 m-1 for bis-porphyrin tweezers 1 and 2, respectively. The higher flexibility of tweezers 2 accounts for the greater association ability. Full photophysical characterization of the complexes, as well as of suitable models, has been performed by means of steady-state and time-resolved optical spectroscopy. Ultrafast luminescence detection and pump-probe transient absorption analysis were used to investigate photoinduced processes within the complexes. The results provide evidence that an electron-transfer process from the bis-porphyrin host to the fullerene guest occurs in both complexes, and a slightly longer lifetime of the charge-separated state is observed in the complex with more flexible host 2.
Davor Margetić, Anamarija Briš, Željko Marinić, and Zhi-Long Chen
Georg Thieme Verlag KG
The Diels–Alder reaction was exploited for the preparation of novel long-wavelength chlorin photodynamic therapy photosensitizers. The styryl group and furan carboxamide substituents were used as diene components in [4+2] cycloaddition functionalizations.
Davor Margetić, Anamarija Briš, Ronald N. Warrener, and Douglas N. Butler
Elsevier BV
Pavle Troselj, Anamarija Briš, Y. Murata and D. Margetić