8 research outputs found
A Convenient and Chemoselective One-Pot Oxidation/Wittig Reaction for the C2-Homologation of Carbohydrate-Derived Glycols.
Evaluation of tuned phosphorus cavitands on catalytic cross-dimerization of terminal alkynes
Wittig-type olefination of alcohols promoted by nickel nanoparticles: synthesis of polymethoxylated and polyhydroxylated stilbenes
Nickel nanoparticles were found to promote the Wittig-type olefination of primary alcohols with phosphorus ylides. The latter can be prepared from the corresponding phosphonium salts with nBuLi or in situ generated with lithium metal. The methodology is especially efficient for the synthesis of stilbenes and is applied in the absence of any additive as ahydrogen acceptor. A new approach to the synthesis of polymethoxylated and polyhydroxylated stilbenes, including resveratrol, DMU-212 and analogues, is presented.Spanish Ministerio de EducaciĂłn y Ciencia (MEC); Grant Number: CTQ2007-65218, CSD2007-00006
Reactivity modulation in container molecules
The encapsulation of a guest within a host molecule can open new pathways of guest reactivity or halt modes of reaction normally observed in solution. Recent findings illustrate how a host's size and shape may alter the regioselectivity and kinetics of guests' reactions within host molecules
Role of Entropy and Autosolvation in Dimerization and Complexation of C 60
The supramolecular chemistry of bowl-shaped heptazinc metallocavitands templated by Schiff base macrocycles has been investigated. Dimerization thermodynamics were probed by 1H NMR spectroscopy in benzene-d6, toluene-d8, and p-xylene-d10 and revealed the process to be entropy-driven and enthalpy-opposed in each solvent. Trends in the experimentally determined enthalpy and entropy values are related to the thermodynamics of solvent autosolvation, solvent molecules being released from the monomeric metallocavitand cavity into the bulk solvent upon dimerization. The relationship established between experimentally measured dimerization thermodynamics and autosolvation data successfully predicts the absence of dimerization in CH2Cl2 and CHCl3 and was used to estimate the number of solvent molecules interacting with the monomeric metallocavitand in solution. Host–guest interactions between heptazinc metallocavitands and fullerene C60 have also been investigated. Interestingly, metallocavitand-C60 interactions are only observed in solvents that facilitate entropy-driven dimerization suggesting entropy and solvent autosolvation may be important in explaining concave-convex interactions