Article
Chemistry, Multidisciplinary
Qi-Kai Kang, Yunzhi Lin, Yuntong Li, Lun Xu, Ke Li, Hang Shi
Summary: A reliable method for accessing phenols and phenyl alkyl ethers via catalytic SNAr reactions has been established in this study, applicable to a broad array of electron-rich and neutral aryl fluorides. Experimental data supporting the mechanism of SNAr reactions are still under exploration, with mechanistic studies and DFT calculations suggesting a stepwise or stepwise-like energy profile. Notably, a rhodium eta(5)-cyclohexadienyl complex intermediate has been isolated with an sp(3)-hybridized carbon bearing both a nucleophile and a leaving group.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Gabriele Micheletti, Robert J. Mayer, Silvia Cino, Carla Boga, Andrea Mazzanti, Armin R. Ofial, Herbert Mayr
Summary: Equilibrium constants for the formation of Wheland complexes from 1,3,5-tris(dialkylamino)benzenes and benzhydrylium ions were determined using photometric method in dichloromethane solution at 20 degrees C. The Lewis basicity of the ring carbons was found to increase in this series.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Oluwakemi A. Oloba-Whenu, Chukwuemeka Isanbor
Summary: This study investigated the reaction mechanism and thermodynamic properties of nucleophilic aromatic substitution reactions of different functionalized dinitrobenzenes and corresponding phenoxy derivatives with aniline under different conditions using computational methods. The formation of Meisenheimer complex intermediates was observed, and their stability depended on the number and position of electron-withdrawing groups on the ring. The overall reactions were exothermic and exergonic. From kinetics calculations, it was found that the initial attack of aniline on dinitrobenzene was the rate-limiting step in acetonitrile, while the decomposition of the intermediate MC was the rate-limiting step in vacuum and toluene. The results suggest the prevalence of a multistep SNAr mechanism and indicate that electron-withdrawing groups can enhance the reaction rate.
Article
Chemistry, Organic
Zi-Hao Jia, Ling-Yan Chen, Hao Zheng, Zhang-Rui Li, Qing-Chun Song, Ya Li
Summary: The study presents a successful synthesis of a series of chiral diarylmethylamines through the BINOL-derived DSI-catalyzed enantioselective aza-Friedel-Crafts reaction. The reaction provides a useful protocol for the direct synthesis of diarylmethylamine derivatives with good yields and excellent enantioselectivities (up to 97% ee).
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Thermodynamics
Chong Wan, Huan Huo, Zhicun Feng, Jianxing Yang, Suhang Chen, Kangzhen Xu
Summary: The thermal behavior of DAOTO was systematically studied using techniques such as differential scanning calorimeter, thermogravimetric analyzer, and thermogravimetric-mass-infrared spectrometry. It was found that DAOTO has good thermal stability and its thermal decomposition process was analyzed. This study provides theoretical support for the application of DAOTO.
JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY
(2023)
Article
Biochemistry & Molecular Biology
Takayuki Ohnuma, Tomoki Taku, Takeshi Nagatani, Atsushi Horii, Shun Imaoka, Tomonari Tanaka
Summary: The chemo-enzymatic synthesis of lacto-N-biose I (LNB) catalyzed by beta-1,3-galactosidase from Bacillus circulans (BgaC) was achieved using 4,6-dimethoxy-1,3,5-triazin-2-yl beta-galactopyranoside (DMT-beta-Gal) and GlcNAc as substrates. BgaC transferred the Gal moiety to the acceptor to produce LNB, with the maximum yield obtained at a ratio of 1:30 for acceptor to donor substrates.
BIOSCIENCE BIOTECHNOLOGY AND BIOCHEMISTRY
(2021)
Article
Chemistry, Organic
Michel Chiarucci, Andrea Mazzanti, Paolo Righi, Giorgio Bencivenni, Michele Mancinelli
Summary: A series of 1,8-bis(1-naphthyl)-naphthalenes with different substituents have been synthesized to investigate noncovalent interactions between stacked arenes. DFT calculations, NMR, and ECD experiments were used to determine the best geometries and understand the role of dispersive and electrostatic contributions. The study revealed that electrostatic contributions greatly influence the interaction energy of the two naphthyl rings, while dispersive forces play a minor role in determining the parallel displaced geometry.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Chiara Volpe, Sara Meninno, Carlo Crescenzi, Michele Mancinelli, Andrea Mazzanti, Alessandra Lattanzi
Summary: This study demonstrates an enantioselective one-pot catalytic strategy for the synthesis of dihydroquinoxalinones, using a combination of catalysts and intermediates to achieve high enantioselectivity in the formation of medicinally relevant heterocycles. The reusability of the organocatalyst and the mechanistic insights into the DROC process provide valuable information for further development of enantioselective synthesis strategies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Michele Di Foggia, Carla Boga, Gabriele Micheletti, Benedetta Nocentini, Paola Taddei
Summary: Hair samples were bleached multiple times and characterized with Raman and IR spectroscopy to assess structural changes and potential development of restoring agents. The use of different spectroscopic techniques allowed for discrimination of information from the hair cortex and cuticle.
Article
Chemistry, Inorganic & Nuclear
Alessandro Di Girolamo, Filippo Monti, Andrea Mazzanti, Elia Matteucci, Nicola Armaroli, Letizia Sambri, Andrea Baschieri
Summary: This study successfully synthesized five cationic iridium(III) complexes using phenyl-triazole derivatives, including the less explored tris-heteroleptic analogues. The redox and emission properties of the complexes can be effectively tuned by different ligands. The complexes equipped with bipyridine ancillary ligand exhibit reversible redox processes and high emission quantum yields, while the complexes equipped with high-field isocyanide ligands display irreversible redox processes and high-energy emission with low quantum yields.
INORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Natalia Calonghi, Carla Boga, Patrizia Nitti, Dario Telese, Silvia Bordoni, Giovanna Farruggia, Fioretta Asaro, Martina Grandi, Chiara Zalambani, Gabriele Micheletti
Summary: Among a series of hydroxystearic acid regioisomers, those with hydroxyl groups at positions 5, 7, and 9 showed growth inhibitory activity against various human tumor cell lines. 5-HSA not only reduced cell proliferation but also induced changes in cell displacement, directionality, and speed in HeLa, HT29, MCF7, and NLF cell lines.
Article
Chemistry, Multidisciplinary
Chiara Portolani, Giovanni Centonze, Sara Luciani, Andrea Pellegrini, Paolo Righi, Andrea Mazzanti, Alessia Ciogli, Andrea Sorato, Giorgio Bencivenni
Summary: The first catalytic enantioselective and diastereoselective synthesis of atropisomeric hydrazides was achieved using a sequential catalysis protocol, providing a stereodivergent approach to enantioenriched atropisomeric hydrazides. The resulting axially chiral hydrazides were obtained directly from commercially available reagents in high yields and with good stereocontrol, demonstrating the effectiveness of this strategy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Gabriele Micheletti, Carla Boga, Chiara Zalambani, Giovanna Farruggia, Erika Esposito, Jessica Fiori, Nicola Rizzardi, Paola Taddei, Michele Di Foggia, Natalia Calonghi
Summary: A series of naphthoquinone derivatives were synthesized through the reaction with N-acetyl-L-cysteine. Compounds 8, 9, and 12 exhibited cytotoxicity against malignant cell lines, while compound 11 showed biological activity at higher IC50 values. Compounds 8 and 11 induced increases in ROS generation.
Article
Chemistry, Inorganic & Nuclear
Andrea Baschieri, Flavia Aleotti, Elia Matteucci, Letizia Sambri, Michele Mancinelli, Andrea Mazzanti, Enrico Leoni, Nicola Armaroli, Filippo Monti
Summary: A new azaborine ligand was synthesized and used as an alternative to common cyclometalating ligands to obtain neutral phosphorescent iridium(III) complexes. The azaborine ligand induces a larger band gap in the complexes and results in a blue-shifted emission wavelength compared to the naphthalene analogues.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Daniel Pecorari, Emanuele Giuliani, Andrea Mazzanti, Stefano Stagni, Valentina Fiorini, Giulia Vigarani, Francesco Zinna, Gennaro Pescitelli, Michele Mancinelli
Summary: Bis-aryl carbazole borane derivatives with emissive properties and axial chirality were synthesized. The resolution of a thermally stable atropisomeric pair (compound 1b), which has a B-C chiral axis, was achieved using chiral stationary-phase high-performance liquid chromatography (CSP-HPLC). The complete photophysical properties of all compounds were measured and simulated using time-dependent density functional theory (TD-DFT) calculations, and circularly polarized luminescence spectra were obtained for the atropisomers of compound 1b, with their absolute configuration determined by a TD-DFT simulation of the electronic circular dichroism (ECD) spectra.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Gabriele Micheletti, Natalia Calonghi, Carla Boga
Summary: Methyl 9-(2-iminothiazol-3(2H)-yl)-9-oxononanoate was synthesized via the Schotten-Baumann reaction between 2-aminothiazole and methyl 9-chloro-9-oxononanoate. The structure of the newly synthesized compound was confirmed using H-1-NMR, C-13-NMR, DEPT, NOE, ESI-MS, FT-IR, and UV-Vis spectroscopy.
Article
Chemistry, Organic
Gabriele Micheletti, Carla Boga
Summary: Methyl 9-(1-methyl-1H-indol-3-yl)-9-oxononanoate was synthesized using Friedel-Crafts acylation between N-methyl indole and methyl 9-chloro-9-oxononanoate. The structure of the newly synthesized compound was elucidated using H-1-NMR, C-13-NMR, NOESY-1D, ESI-MS, FT-IR, and UV-Vis spectroscopy.
Article
Biochemistry & Molecular Biology
Silvia Bordoni, Riccardo Tarroni, Magda Monari, Stefano Cerini, Fabio Battaglia, Gabriele Micheletti, Carla Boga, Giacomo Drius
Summary: The reaction between Ru complex 1 and thymine acetic acid (THAcH) unexpectedly gives rise to macrocyclic dimer 4 and doubly coordinated species 5. By considering the energetics calculated by DFT, two possible reaction paths were proposed. The stable symmetric 14-membered binuclear macrocycle 4 is formed through self-aggregation, whereas species 2 achieves additional stabilization through k(2)(N,O) thymine heteroleptic side-chelation.
Article
Biochemistry & Molecular Biology
Giacomo Drius, Silvia Bordoni, Carla Boga, Magda Monari, Jessica Fiori, Erika Esposito, Chiara Zalambani, Luca Pincigher, Giovanna Farruggia, Natalia Calonghi, Gabriele Micheletti
Summary: In this study, three Ru(II) complexes containing hydroxy stearic acids (HSAs) were successfully synthesized and evaluated for their synergistic effects between the known antitumor activity of HSA bio-ligands and the metal center. The results showed that Ru-7-HSA and Ru-9-HSA complexes exhibited biological activity, with Ru-9-HSA showing increased antitumor activity on colon cancer cells, HT29.
Article
Chemistry, Physical
Flavia Aleotti, Vasilis Petropoulos, Hannah Van Overeem, Michele Pettini, Michele Mancinelli, Daniel Pecorari, Margherita Maiuri, Riccardo Medri, Andrea Mazzanti, Fabrizio Preda, Antonio Perri, Dario Polli, Irene Conti, Giulio Cerullo, Marco Garavelli
Summary: In this study, we investigate the influence of the structural features of photoactive azobenzene derivatives on the behavior of the photoexcited state and the yield of the trans/cis photoisomerization process. Our results demonstrate that intramolecular H-bonds stabilize the trans isomer and hinder the photoisomerization process, while the involvement of the azo group in keto-enol tautomerism promotes productive torsional motion.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Inorganic & Nuclear
Jing Tu, Daniele Veclani, Filippo Monti, Andrea Mazzanti, Letizia Sambri, Nicola Armaroli, Andrea Baschieri
Summary: A new synthetic method has been developed for the preparation of unexpected emissive iridium(iii) complexes (A and B). The structures and reaction mechanisms of these complexes were characterized and analyzed. The findings of higher photoluminescence quantum yield in complex A compared to known analogues provide a potential pathway for the direct synthesis of luminescent complexes.
DALTON TRANSACTIONS
(2023)
