Reactivity of Glutaconamides Within [2]Rotaxanes: Mechanical Bond Controlled Chemoselective Synthesis of Highly Reactive α-Ketoamides and their Light-Triggered Cyclization

Glutaconamide-based [2]rotaxanes are efficiently oxidized to the respective interlocked α-ketoamides, whereas their non-interlocked threads afford hydroxycyclohexene tetraamides under similar reaction conditions. These results showcase the mechanically interlocking of highly reactive substrates as a powerful tool for controlling their chemical behavior. Inside the macrocycle and under irradiation with light, the α-ketoamide threads convert, in a divergent manner, into the corresponding interlocked hydroxy-β-lactams or oxazolidinones by two modes of Norrish/Yang type-II intramolecular cyclizations, processes that are efficiently chemocontrolled by the mechanical bond

Mechanically Planar-to-Point Chirality Transmission in [2]Rotaxanes

© 2024. The authors. This document is made available under the CC-BY 4.0 license http://creativecommons.org/licenses/by /4.0/ This document is the published version of a published work that appeared in final form in Journal of the American Chemical Society (JACS). To access the final work, see DOI: https://doi.org/10.1021/jacs.3c11611Herein we describe an effective transmission of chirality, from mechanically planar chirality to point chirality, in hydrogen-bonded [2]rotaxanes. A highly selective mono-N-methylation of one (out of four) amide N atom at the macrocyclic counterpart of starting achiral rotaxanes generates mechanically planar chirality. Followed by chiral resolution, both enantiomers were subjected to a base-promoted intramolecular cyclization, where their interlocked threads were transformed into new lactam moieties. As a matter of fact, the mechanically planar chiral information was effectively transferred to the resulting stereocenters (covalent chirality) of the newly formed heterocycles. Upon removing the entwined macrocycle, the final lactams were obtained with high enantiopurity

Dimerization of tris (o-ureidobenzyl) amines: a novel class of aggregates

Dimeric aggregates are formed by the assembly of two tripodal moieties which are held together, both in solution and in the solid state, by a belt of 6 hydrogen-bonded urea functions

Novel Capsular Aggregates from Flexible Tripodal Triureas with Cs Symmetry

Tris(2‐ and 3‐ureidobenzyl)amines with Cs symmetry self‐assemble in solution forming mixtures of regioisomeric capsular aggregates, one of which is chiral and the other centrosymmetric. Under certain conditions, a predominance of the centrosymmetric regioisomer is found before equilibrium, that is, a mixture close to the statistical ratio of the two species is reached. In the solid state, there is a preference for the centrosymmetric capsules. Molecular models of both regioisomeric aggregates have been built and analyzed for comparison. Guests inside capsules formed by self‐assembly of desymmetrized tris(3‐ureidobenzyl)amines feel different magnetic environments, depending on whether they are inside a chiral or an achiral regioisomeric container. Of special significance are the experiments with a more flexible triurea endowed with an ureidopropylic arm, which self‐assembles with the same efficiency as the more rigid tris(ureidobenzyl)amines

Automatic Heart Sounds Segmentation based on the Correlation Coefficients Matrix for Similar Cardiac Cycles Identification

This paper proposes a novel automatic heart sounds segmentation method for deployment in heart valve defect diagnosis. The method is based on the correlation coefficients matrix, calculated between all the heart cycles for similarity identification. Firstly, fundamental heart sounds (S1 and S2) in the presence of extra gallop sounds such as S3 and/or S4 and murmurs are localized with more accuracy. Secondly, two similarity-based filtering approaches (using time and time-frequency domains, respectively) for correlated heart cycles identification are proposed and evaluated in the context of professional clinical auscultated heart sounds of adult patients. Results show the superiority of the novel time-frequency method proposed here particularly in the presence of extra gallop sounds

(Z)-(1,2-Dichloro­vin­yl)diphenyl­phosphine oxide

The title compound, C14H11Cl2OP, was synthesized by the reaction of diphenyl­phosphine oxide with 1,2-dichloro­ethyne under CuI catalysis. The reaction provided the Z isomer regioselectively. Two O—P—C bond angles [114.3 (1) and 112.5 (1)°] are significantly larger than the C—P—C [107.7 (1), 105.6 (1) and 106.6 (1)°] and another O—P—C angle [109.5 (1)°], indicating significant distortion of the tetra­hedral configuration of the P atom. In the crystal, mol­ecules are linked by weak inter­molecular C—H⋯O hydrogen bonds into centrosymmetric dimers, which are connected by further C—H⋯O inter­actions into chains along [101]

Theoretical studies of 31P NMR spectral properties of phosphanes and related compounds in solution

Selected theoretical methods, basis sets and solvation models have been tested in their ability to predict 31P NMR chemical shifts of large phosphorous-containing molecular systems in solution. The most efficient strategy was found to involve NMR shift calculations at the GIAO-MPW1K/6-311++G(2d,2p)//MPW1K/6-31G(d) level in combination with a dual solvation model including the explicit consideration of single solvent molecules and a continuum (PCM) solvation model. For larger systems it has also been established that reliable 31P shift predictions require Boltzmann averaging over all accessible conformations in solution

One-pot Cannizzaro cascade synthesis of ortho-Fused Cycloocta-2,5-dien-1-ones from 2-Bromo(hetero)aryl aldehydes

An intramolecular Cannizzaro-type hydride transfer to an in situ prepared allene enables the synthesis of orthofused 4-substituted cycloocta-2,5-dien-1-ones with unprecedented technical ease for an eight-ring carboannulation. Various derivatives could be obtained from commercially available (hetero)aryl aldehydes, trimethylsilylacetylene, and simple propargyl chlorides in good yields

Homogeneous and heterogeneous catalysts for multicomponent reactions

[EN] Organic synthesis performed through multicomponent reactions is an attractive area of research in organic chemistry. Multicomponent reactions involve more than two starting reagents that couple in an exclusive ordered mode under the same reaction conditions to form a single product which contains the essential parts of the starting materials. Multicomponent reactions are powerful tools in modern drug discovery processes, because they are an important source of molecular diversity, allowing rapid, automated and high throughput generation of organic compounds. This review aims to illustrate progress in a large variety of catalyzed multicomponent reactions performed with acid, base and metal heterogeneous and homogeneous catalysts. Within each type of multicomponent approach, relevant products that can be obtained and their interest for industrial applications are presented.The authors wish to gratefully acknowledge the Generalitat Valenciana for the financial support in the project CONSOLIDER-INGENIO 2010 (CSD2009-00050)Climent Olmedo, MJ.; Corma Canós, A.; Iborra Chornet, S. (2012). Homogeneous and heterogeneous catalysts for multicomponent reactions. RSC Advances. 2(1):16-58. https://doi.org/10.1039/c1ra00807bS16582