Spironolactone and its Complexes with β-cyclodextrin: Modern NMR Characterization and Structural DFTB-SCC Calculations

In the present work, inclusion complexes of spironolactone (SP) with β-cyclodextrin (β-CD) in solid phase and aqueous solution were studied by solubility methods, NMR spectroscopy and thermal analysis. The results showed different kinds of complexations when freeze-drying and kneading methods were used. The freeze-drying product (1:1, SP:β-CD) showed lower degree of complexation and stability than the (1:2, SP:β-CD) compound obtained by kneading method. The spironolactone molecule was also studied by NMR spectroscopy at 400 MHz. The chemical shifts of all spironolactone atoms and their inclusion compounds were assigned. Extensive use of 1D and 2D NMR techniques, including ROESY experiment, allowed verifying the position of the spironolactone molecule inside the cyclodextrin cavity in both situations. In addition, DFTB-SCC quantum mechanical calculations of the inclusion compounds were performed. The predicted structural properties are in good agreement with ROESY NMR results.     

The through-space transmission of 13C19F coupling constants via an intermediate bond: A polarization propagator analysis

Inner projections of the polarization propagator were used to study the indirect through-space transmission of the Fermi contact term of CF couplings via a CX (X = F, H) intermediate bond. When X = H a large capability for transmitting this component is observed. But for X = F a notable inhibition of this transmission mechanism is observed. The role of the fluorine lone pairs in this behaviour is discussed.     

General approach to glycosidase inhibitors. Enantioselective synthesis of deoxymannojirimycin and swainsonine

[reaction: see text] Deoxymannojirimycin (2) and swainsonine (4) have been synthesized from each enantiomer of the same bicyclic carbamate precursor 7. The key intermediate was prepared by a simple and efficient three-step synthesis involving RCM of the diene 8, which in turn is easily accessible in any configuration from enantiomerically enriched 2,3-epoxy-4-penten-1-ol 9.     

Upper bound for the magnetic force gradient in graphite

In this work we investigate possible ferromagnetic order on the graphite surface by using magnetic force microscopy (MFM). Our data show that the tip-sample interaction along the steps is independent of an external magnetic field. Moreover, by combining kelvin probe force microscopy and MFM, we are able to separate the electrostatic and magnetic interactions along the steps obtaining an upper bound for the magnetic force gradient of 16 μN/m. Our experiments suggest the absence of ferromagnetic signal in graphite at room temperature.     

Role of the Bridge in Photoinduced Electron Transfer in Porphyrin–Fullerene Dyads

The role of π‐conjugated molecular bridges in through‐space and through‐bond electron transfer is studied by comparing two porphyrin–fullerene donor–acceptor (D–A) dyads. One dyad, ZnP–Ph–C₆₀ (ZnP=zinc porphyrin), incorporates a phenyl bridge between D and A and behaves very similarly to analogous dyads studied previously. The second dyad, ZnP–EDOTV–C₆₀, introduces an additional 3,4‐ethylenedioxythienylvinylene (EDOTV) unit into the conjugated bridge, which increases the distance between D and A, but, at the same time, provides increased electronic communication between them. Two essential outcomes that result from the introduction of the EDOTV unit in the bridge are as follows: 1) faster charge recombination, which indicates enhanced electronic coupling between the charge‐separated and ground electronic states; and 2) the disappearance of the intramolecular exciplex, which mediates photoinduced charge separation in the ZnP–Ph–C₆₀ dyad. The latter can be interpreted as a gradual decrease in electronic coupling between locally excited singlet states of D and A when introducing the EDOTV unit into the D–A bridge.     

Gedunin,ad-seco limonoid

Chloroform/Methanol extraction of the bark ofCedrela salvadorensis (Meliaceae), followed by chromatography afforded the crystalline C₂₈H₃₄O₇ terpene. The structure first proposed by spectroscopy is confirmed by this X-ray analysis as 7-acetyloxy-14,15:21,23-diepoxy-4,4,8-trimethyl-d-homo-24-nor-17-oxachola-1,20,22-triene-3,16,-dione. The title compound crystallized in the orthorhombic space groupP2₁2₁2₁ with unit cell parametersa=10.243(2),b=13.356(3) andc=18.058(4) Å. The molecule is comprised of a six-membered tetracyclic skeleton, with a circular arc overall conformation. No intermolecular hydrogen bonding is indicated.     

Cyclotetraveratrylene and its benzene solvate

The title compound crystallizes in a solvent-free form and also includes solvent molecules. The X-ray structure analysis reveals that in the both crystal forms the cyclododecatetraene ring in the host molecules adopts a sofa conformation. The guest molecules occupy the channels formed among columns of stacked host molecules.Contribution No. 1452 of Instituto de Química, UNAM.     

Synthesis of Bifunctional Allylic Compounds by Using Cyclopropenes as Functionalized Allyl Equivalents

The synthesis of uncommon bifunctional allylic derivatives bearing a silane and an alcohol within the same allylic framework is reported. This method relies on the coupling of hydrosilanes with substituted and functionalized cyclopropenes, which deliver the allyl fragment. Rhodium(II) catalysts provide regioselective access to vinyl carbene intermediates, which easily undergo Si?H bond insertions. The transformation occurs with complete atom economy and shows a remarkably broad scope, including a intramolecular version for the synthesis of cyclic O?Si‐linked compounds as well as the synthesis of the corresponding allyl amines.