Search results for "Stereochemistry"
showing 10 items of 4831 documents
Helical supramolecular polymerization of C3-symmetric amides and retroamides: on the origin of cooperativity and handedness.
2016
The cooperative supramolecular polymerization of 1 and 2 yields P- or M-type helical aggregates depending on the absolute configuration (S or R) of the stereogenic centres attached to the side chains. The connectivity of the amide group does not affect the handedness of the helical aggregates, but determines a larger cooperativity for retroamides 1.
Catalytic enantioselective aza-Reformatsky reaction with seven-membered cyclic imines dibenzo[b,f][1,4]oxazepines
2017
A catalytic enantioselective aza-Reformatsky reaction is reported with cyclic dibenzo[b,f][1,4]oxazepines and ethyl iodoacetate leading to the synthesis of chiral ethyl 2-(10,11-dihydrodibenzo[b,f][1,4]oxazepin-11-yl)acetate derivatives with excellent yields and high enantioselectivities (up to 98% yield and 97 : 3 er) using a readily available diaryl prolinol L4 as the chiral ligand and Me2Zn as the zinc source under an air atmosphere. Furthermore, different transformations were carried out with the corresponding chiral β-amino esters, preserving in all cases the optical purity.
Catalytic Asymmetric Reactions Involving the Seven-Membered Cyclic Imine Moieties Present in Dibenzo[b,f][1,4]oxazepines
2017
The dibenzo[b,f][1,4]oxazepine scaffold is a privileged structure in medicinal chemistry that displays a wide variety of biological and pharmacological activities. However, catalytic asymmetric methodologies for the synthesis of chiral dibenzo[b,f][1,4]oxazepine derivatives are scarce in the literature. This microreview presents an overview of enantioselective reactions in which these cyclic seven-membered imines are used as electrophiles, including their substrate scope, limitations and application to the synthesis of related compounds.
Conformational Control of Metallocene Backbone by Cyclopentadienyl Ring Substitution: a New Concept in Polyphosphane Ligands Evidenced by “Through-Sp…
2009
The present study deals with the conformational control of the metallocene backbone within ferrocenyl polyphosphane ligands and their performance in the highly topical palladium-catalyzed heteroaromatics arylation by direct C−H activation. New substituted cyclopentadienyl rings were synthesized, which allowed the assembling of original tri- and diphosphanes. The bulky cyclopentadienyl lithium salts diphenylphosphino-3-(triphenyl)methylcyclopentadienyllithium (4) and 1,2-bis(diphenylphosphino)-4-(triphenyl)methylcyclopentadienyllithium (5) were prepared in excellent yield. The assembling of these new hindered cyclopentadienyl salts (Cp) with other Cp fragments was performed in order to prepa…
Cross-Metathesis/Intramolecular (Hetero-)Michael Addition: A Convenient Sequence for the Generation of Carbo- and Heterocycles
2017
The high stability and functional group compatibility of ruthenium carbene complexes confer them a great ability to catalyze domino processes. For this reason, the combination of metathesis reactions with additional transformations in a domino fashion has been exploited extensively, with the result of expanding the utility of ruthenium carbene complexes beyond that of just olefin metathesis. Among those domino processes, it is worth mentioning the sequence of cross-metathesis/intramolecular Michael addition, which allows for the generation of a wide variety of carbo- and heterocycles in a very simple manner, taking advantage of the benefits of domino reactions. Carbon-, oxygen- and nitrogen…
Molybdenum Pentachloride Mediated Synthesis of Spirocyclic Compounds by Intramolecular Oxidative Coupling
2015
The oxidative treatment of (m)ethyl 2-aryl cinnamates equipped with methoxy groups in position 4 of the phenyl moiety promote the formation of cyclohexadienone substructures. This dealkylative oxidative C–C coupling gives access to spirocyclic compounds and avoids the construction of the corresponding phenanthrenes. Furthermore, the transformation can be expanded to other spirocyclic systems.
Substituent effect on the σ- and π-electron structure of the nitro group and the ring in meta- and para-substituted nitrobenzenes
2017
An application of quantum chemical modeling allowed us to investigate a substituent effect on a σ and π electron structure of a ring and the nitro group in a series of meta- and para-X-substituted nitrobenzene derivatives (X = NMe2, NHMe, NH2, OH, OMe, Me, H, F, Cl, CF3, CN, CHO, COMe, CONH2, COOH, NO2, and NO). The obtained pEDA and sEDA parameters (the π- and σ-electron structure characteristics of a given planar fragment of the system obtained by the summation of π- and σ-orbital occupancies, respectively) of the NO2 group and the benzene ring allowed us to reveal the impact of the substituents on their mutual relations as well as to analyze them from the viewpoint of substituent charact…
Controlling the Host-Guest Interaction Mode through a Redox Stimulus
2017
International audience; A proof-of-concept related to the redox-control of the binding/releasing process in a host-guest system is achieved by designing a neutral and robust Pt-based redox-active metallacage involving two extended-tetrathiafulvalene (exTTF) ligands. When neutral, the cage is able to bind a planar polyaromatic guest (coronene). Remarkably, the chemical or electrochemical oxidation of the host-guest complex leads to the reversible expulsion of the guest outside the cavity, which is assigned to a drastic change of the host-guest interaction mode, illustrating the key role of counteranions along the exchange process. The reversible process is supported by various experimental d…
Recognition of self-assembled water-nitrate cluster in a Co(III)-2,2′-bipyridine host: Synthesis, X-ray structure, DNA cleavage, molecular docking an…
2016
A mononuclear cobalt(III) complex [Co(bpy)2Cl2]NO3⋅2H2O (1) (bpy = 2,2′-bipyridine) has been synthesized and crystallographically characterized. Self-assembly of the lattice water molecules from rectangular tetrameric water cluster interacts with nitrate anion along the c-axis forming a six membered hexagonal water-nitrate cluster. It presents a new mode of association of water molecules with nitrate molecules which is not predicted theoretically or found experimentally. The molecule effectively cleaves bacterial genomic DNA and shows important cytotoxicity against human hepatocarcinoma cell (HepG2).
Extending the halogen-bonded supramolecular synthon concept to 1,3,4-oxadiazole derivatives
2016
A series of five crystal structures of 1:1 halogen-bonded complexes were obtained from 4-[5-(4-alkoxyphenyl)-1,3,4-oxadiazole-2-yl]pyridine and 1,3,5-trifluorotriiodobenzene. Electronic structure calculations show that the N(oxadiazole)⋯I interaction in the new synthon is as strong as the classic N(pyridine)⋯I interaction. Oxygen to sulfur atom subsitution on the oxadiazole ring results in a different supramolecular packing where the N(pyridine)⋯I interaction is favored, which could be rationalized by the changes in the molecular electrostatic potential predicted from the theoretical calculations.