We present herein the application of a lithium anthraquinoid in the catalytic synthesis of cyclic PLA, showing that the aggregation plays a critical role in cyclic vs. linear selectivity.
A new Y-based metal−organic framework (MOF) GR-MOF-6 with a chemical formula of {[YL(DMF) 2 ]•(DMF)} n {H 3 L = 5-[(4-carboxyphenyl)ethynyl] isophthalic acid; DMF = N,N-dimethylfor-mamide} has been prepared by a solvothermal route. Structural characterization reveals that this novel material is a three-dimensional MOF in which the coordination of the tritopic ligand to Y(III) metal ions leads to an intercrossing channel system extending over three dimensions. This material has proven to be a very efficient catalyst in the cyanosilylation of carbonyls, ranking second in catalytic activity among the reported rare earth metal-based MOFs described so far but with the lowest required catalyst loading. In addition, its electrophoretic behavior has been studied in depth, providing a zero-charge point between pH 4 and 5, a peak electrophoretic mobility of −1.553 μm cm V −1 s −1 , and a ζ potential of −19.8 mV at pH 10.
We
have proven that the biomimetic-like synthesis of cannabinoids
from citral and the corresponding phenolic counterpart may well be
carried out using water as a solvent. The influence of different additives
such as surfactants was also analyzed. Rationalization of the reaction
mode and regiochemistry of the processes were provided in terms of
“on water” and “in water” reactions. The
same reactions were conducted in organic media using Ga(III) salts
as catalysts. Worthy of being underlined, an unprecedented formal
[2+2+2] process was found to occur between two citral molecules and
the corresponding phenolic species in both aqueous and organic environments.
Computational studies were performed in order to gain a comprehensive
mechanistic and energetic understanding of the different steps of
this singular process. Finally, the influence of SDS micelles in the
chemical behavior of olivetol and citral was also pursued using PGSE
diffusion and NOESY NMR studies. These data permitted to tentatively
propose the existence of a mixed micelle between olivetol and SDS
assemblies.
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