Interlocked molecules, such as rotaxanes, catenanes, and molecular knots, offer conceptually new possibilities for the generation of chiral chemosensors catalysts. Due to presence mechanical or topological bond, interlocked molecules can be used design functional systems with unprecedented features, switchability deep binding cavities. In addition, classical elements chirality supplemented chirality, which have so far only scarcely been employed sources stereoselective applications. This...

Heterobifunctional rotaxanes serve as efficient catalysts for the addition of malonates to Michael acceptors. We report a series four different heterobifunctional rotaxanes, featuring an amine-based thread and chiral 1,1'-binaphthyl-phosphoric-acid-based macrocycle. High-level DFT calculations provided mechanistic insights enabled rational catalyst improvements, leading interlocked that surpass their non-interlocked counterparts in terms reaction rates stereoselectivities.

Recently, the development of rotaxane-based architectures for biological applications has started to attract interest. In this short review, we summarize main advances that have been realized in burgeoning area research, including design squaraine-rotaxane dyes optical bioimaging applications, host-rotaxanes as cellular transport agents, enzyme-responsive rotaxanes and mechanized mesoporous silica nanoparticles coated with “nanovalves” drug delivery systems. Récemment, le développement de...

Abstract Inspired by interlocked oligonucleotides, peptides and knotted proteins, synthetic systems where a macrocycle cages bioactive species that is “switched on” breaking the mechanical bond have been reported. However, to date, each example uses bespoke chemical design. Here we present platform approach mechanically caged structures wherein single precursor diversified at late stage include range of trigger units control ring opening in response enzymatic, chemical, or photochemical...

Abstract Heterobifunctional rotaxanes serve as efficient catalysts for the addition of malonates to Michael acceptors. We report a series four different heterobifunctional rotaxanes, featuring an amine‐based thread and chiral 1,1′‐binaphthyl‐phosphoric‐acid‐based macrocycle. High‐level DFT calculations provided mechanistic insights enabled rational catalyst improvements, leading interlocked that surpass their non‐interlocked counterparts in terms reaction rates stereoselectivities.

Despite the impressive number of interlocked molecules described in literature over past 30 years, only a few stereoselective syntheses mechanically chiral rotaxanes have been reported so far. In this study, we present first diastereoselective synthesis planar [1]rotaxanes, that has achieved using active template Cu-mediated alkyne-azide cycloaddition reaction. This synthetic method applied to preparation [1]rotaxane bearing labile stopper can then be substituted without disruption...

Inspired by interlocked oligonucleotides, peptides and knotted proteins, synthetic systems where a macrocycle cages bioactive species that is “switched on” breaking the mechanical bond have been reported. However, to date, each example uses bespoke chemical design. Here we present platform approach mechanically caged structures wherein single precursor diversified at late stage include range of trigger units control ring opening in response enzymatic, chemical, or photochemical stimuli. We...

Inspired by interlocked oligonucleotides, peptides and knotted proteins, synthetic systems where a macrocycle cages bioactive species that is “switched on” breaking the mechanical bond have been reported. However, to date, each example uses bespoke chemical design. Here we present platform approach mechanically caged structures wherein single precursor diversified at late stage include range of trigger units control ring opening in response enzymatic, chemical, or photochemical stimuli. We...

Abstract The mechanical bond is emerging as a novel design element in catalyst development. Here, we report series of 1,1’‐binaphthyl‐2,2’‐diol (BINOL) based catalysts which the number interlocked macrocycles varied. Unsurprisingly, have profound steric influence on catalytic performance these molecules. However, enantioselective transformations examined, are detrimental to stereoselectivity whereas lactide polymerization, they increase molecular weight polymeric product.

Abstract Inspired by interlocked oligonucleotides, peptides and knotted proteins, synthetic systems where a macrocycle cages bioactive species that is “switched on” breaking the mechanical bond have been reported. However, to date, each example uses bespoke chemical design. Here we present platform approach mechanically caged structures wherein single precursor diversified at late stage include range of trigger units control ring opening in response enzymatic, chemical, or photochemical...

Abstract The experimental vibrational circular dichroism (VCD) and electronic (ECD) spectra were measured for the enantiomers of [1]rotaxane 1 . These have been analyzed using predicted VCD ECD ( S , R mp ) or diastereomers density functional theory. This comparison allowed a definitive assignment absolute configuration

Abstract Rotaxane und Catenane lassen sich inzwischen in guten Ausbeuten herstellen – auch wegen neuer Synthesestrategien wie der Active‐Template‐Methode. Diese nutzt Metalle Kupfer(I), zwar nicht nur als Templatbildner, sondern Katalysator.

Heterobifunktionelle Rotaxane wirken als Katalysatoren für die Addition von Malonaten an Michael-Akzeptoren. J. Niemeyer et al. präsentieren in ihrem Forschungsartikel auf S. 5140 eine Serie heterobifunktioneller mit einer Amin-basierten Achse und einem chiralen Phosphorsäure-basierten Makrocyclus. Rationale Katalysatorverbesserungen Unterstützung durch DFT-Rechnungen führten zu verzahnten Katalysatoren, ihre nichtverzahnten Gegenstücke bezüglich der Reaktionsgeschwindigkeiten...

To consider the topology of a molecule its structure is reduced to labelled vertices (the atoms) and edges (bonds between them) generate molecular graph . If only covalent bonding interactions are included , such graphs like structural diagrams commonly employed describe molecules, except that in topological terms, atomic geometry largely irrelevant; most molecules can be represented as two-dimensional network stereogenic units topologically irrelevant. In 1960, Wasserman synthesized which...

To consider the topology of a molecule its structure is reduced to labelled vertices (the atoms) and edges (bonds between them) generate molecular graph . If only covalent bonding interactions are included , such graphs like structural diagrams commonly employed describe molecules, except that in topological terms, atomic geometry largely irrelevant; most molecules can be represented as two-dimensional network stereogenic units topologically irrelevant. In 1960, Wasserman synthesized which...

Abstract To consider the topology of a molecule, its structure is reduced to labelled vertices (the atoms) and edges (bonds between them) generate molecular graph. If only covalent bonding interactions are included, such graphs like structural diagrams commonly employed by chemists atomic geometry irrelevant; most molecules can be represented as two-dimensional network stereoisomers topologically identical. In 1960, Wasserman synthesized molecule in which two rings held together chain,...