As the benzene 1,3,5-tricarboxamide (BTA) moiety is commonly used as central assembling unit for construction of functionalized supramolecular architectures, strategies to tailor nature and stability BTA assemblies are needed. The assembly properties a library structurally simple BTAs derived from amino dodecyl esters (ester BTAs, 13 members) have been studied, either in bulk or cyclohexane solutions, by means series analytical methods (NMR, DSC, POM, FT-IR, UV-Vis, CD, ITC, high-sensitivity...

Ferrociphenols, especially those possessing a heterocycle at the terminus of an aliphatic chain, display strong anticancer activity through novel redox mechanism that generates active metabolites such as quinone methides (QMs). X-ray crystallography and UV/Vis spectroscopy reveal specific lone pair (lp)-π interaction between carbonyl group imide motif QM plays important role in exceptional cytotoxic behaviour their imido-ferrociphenol precursors. This intramolecular lp-π markedly enhanced...

Discrete metallomacrocycles are attractive scaffolds for the formation of complex supramolecular architectures with emergent properties. We herein describe hierarchical nanostructures using preformed by coordination-driven self-assembly a covalent organic-inorganic polyoxometalate (POM)-based hybrid. In this system, we take advantage presence charged subunits (POM, metal linker, and counterions) within metallomacrocycles, which drive their aggregation through intermolecular electrostatic...

Novel 2,5-meso-pyrrolidines have been straightforwardly synthesized from readily available symmetrical double Michael acceptors. The key step rested on an aza-Michael addition of primary alkylamines to bis-enones. Competitive Rauhut–Currier and reactions highlighted in protic solvent. Ultrasound activation associated with solvent-free conditions led the expected pyrrolidines quantitative yields excellent stereoselectivities. optimized extended sonochemical synthesis pyrrolidine Lobelia...

A heterochiral 1,3,5-benzene tricarboxamide (BTA) monomer, derived from valine dodecyl ester, forms long rods in cyclohexane whilst its homochiral analogue assembles into dimers only at the same concentration. This highly original assembly behaviour is related to destabilization of dimeric structure containing two monomers as corroborated by a combined experimental and computational study.

Abstract Squalenoyl conjugates of semaxanib and sunitinib, two potent antiangiogenic (pyrrolyl)methylidenyl‐substituted oxindole multitarget tyrosine kinase inhibitors, were synthesized with a hemiaminal‐based pH‐sensitive linker. The prodrugs prepared according to three‐step sequence involving (i) N ‐alkylation chloromethoxy‐triisopropylsilane; (ii) desilylation; (iii) acylation trisnorsqualenic acid. These squalenoyl found self‐assemble into nanoassemblies in aqueous media without the need...

Abstract Aggregation of supramolecular helices, for example through interdigitation their alkyl side chains or more directional interactions, leads to hierarchical architectures with original structural and chiroptical properties. However, when a chiral monomer (the “sergeant”) is introduced as minor component in these assemblies composed majority achiral monomers “soldiers”), it not clear how the aggregation changes ability sergeant induce preferential helicity polymer main chain so‐called...

The step-economical synthesis of lobelanine involving a ring closing double aza-Michael (RCDAM) reaction is revisited and successfully extended to the various configurationally more stable analogues.

Abstract While the generation of aryl radicals by photoredox catalysis under reductive conditions is well documented, it has remained challenging an oxidative pathway. Because easy photo‐oxidation alkyl bis‐catecholato silicates, a general study phenyl silicates bearing substituted catecholate ligands been achieved. The newly synthesized have fully characterized, and their reactivity explored. It was found that, thanks to substitution moiety, notably with 4‐cyanocatecholato ligand, radical...

Abstract We report herein a new family of carbene ligands based on an indolizine‐ylidene (Indolizy) moiety. The corresponding gold(I) complexes are easily obtained from the gold(I)‐promoted cyclization allenylpyridine precursors. Evaluation electronic properties by experimental methods and also DFT calculations confirms strong σ‐donating π‐accepting these ligands. Cationization generates catalytic species that trigger diverse reactions (poly)unsaturated When armed with methylene phosphine...

A novel bimodal fluorescent and fluorinated substrate of the chymotrypsin-like proteolytic activity has been developed.

High-symmetry (left) and low-symmetry (<italic>e.g.</italic> that on the right) conformations of benzene-1,3,5-tricarboxamide dimers derived from glycine alkyl esters are in rapid exchange solution through amide/ester competition for binding N–H donors.

The field of iron catalysis often faces hurdles in accommodating its transient and unstable low-valent intermediates. By harnessing the noninnocent character commercial bathocuproine ligand, we managed to develop a reliable functionalization alkynes with primary, secondary, tertiary silanes but also germanium hydrides, catalyzed by complex. robustness catalyst enabled gram-scale synthesis vinylsilanes, low catalytic loading, one-pot, hetero, bis-hydrosilylation, high steric build-up....

Abstract Switchable tandem intramolecular aza‐Michael/Michael and double aza‐Michael reactions allow the oriented synthesis of highly functionalised cyclic skeletons. Conjugate addition deactivated anilines triggers chemo‐ stereo‐divergent ring‐closure reaction pathways with a striking selectivity depending on conditions.

Abstract Adding a complementary achiral monomer to polymers embedding mixture of enantiopure monomers (the “sergeants”) and “soldiers”) is expected decrease the optical purity polymer main chain. This study reports influence such benzene‐1,3,5‐tricarboxamide (BTA) additives on properties “sergeants‐and‐soldiers” mixtures composed an BTA ligand coordinated copper monomer. Whilst N , N’ ’’‐tris(octyl)benzene‐1,3,5‐tricarboxamide ( C8 ) shows no significant improvement in term...

The double aza-Michael reaction of enantiopure primary amines on bis α,β-unsaturated diesters has been studied under various activating conditions.High pressure allowed a rapid and efficient access to meso-2,5-disubstituted pyrrolidines.equivalents is known be the most route prepare β-amino acids. 3However, applied dialkyl (E,E)-octa-2,6-dienoates, addition lithium amide led homochiral aminocyclopentane via tandem conjugate addition-intramolecular cyclisation process. 4O MeO 2 C CO Me NH H Ph

Asymmetric Michael addition of chiral 2-fluoroenaminoesters derived from (S)-1-phenylethylamine to α-substituted methyl acrylate leads diastereomeric γ-substituted γ-fluoroglutamate precursors. The tertiary center bearing the amino acid function in its natural configuration is generated with a high level stereocontrol contrast quaternary carbon center. Diastereomeric γ-fluoroglutamates were efficiently separated and isolated as thioketal derivatives harboring very good enantioselectivity....

Abstract Ferrociphenols, especially those possessing a heterocycle at the terminus of an aliphatic chain, display strong anticancer activity through novel redox mechanism that generates active metabolites such as quinone methides (QMs). X‐ray crystallography and UV/Vis spectroscopy reveal specific lone pair (lp)–π interaction between carbonyl group imide motif QM plays important role in exceptional cytotoxic behaviour their imido‐ferrociphenol precursors. This intramolecular lp–π markedly...

Abstract Diastereomeric reduction of nonactivated, hindered β‐keto and chiral β‐iminoesters are described. The influence a α‐stereocontrolled center on the efficiency stereoselectivity was studied. Reaction conditions were optimized to synthesize β‐hydroxy‐ β‐aminoesters in good yields. In case β‐iminoesters, matched/mismatched diastereomeric pairs has been assessed. Chirality, 2011. © 2010 Wiley‐Liss, Inc.

Abstract Neutral cyclometallated Pt(II) complexes [(C^N t −Bu ^N )Pt−R] ( 4 – 5 ) containing a bis‐urea alkynyl (R) ligand have been prepared and fully characterized. The dichotomous nature of makes it difficult to anticipate which interactions (hydrogen bonds, π−π stacking Pt⋅⋅⋅Pt) will dominate their assembly process. aggregation properties were thus probed by multifarious analytical (UV/Vis, FT‐IR, NMR, MS, CD, emission) computational (DFT, TD‐DFT) techniques. CD analyses...

Abstract We report herein a new family of carbene ligands based on an indolizine‐ylidene (Indolizy) moiety. The corresponding gold(I) complexes are easily obtained from the gold(I)‐promoted cyclization allenylpyridine precursors. Evaluation electronic properties by experimental methods and also DFT calculations confirms strong σ‐donating π‐accepting these ligands. Cationization generates catalytic species that trigger diverse reactions (poly)unsaturated When armed with methylene phosphine...

Abstract Conjugate addition of deactivated anilines triggers chemo‐ and stereo‐divergent ring‐closure reaction pathways with a striking selectivity depending on conditions.