RESUMO
The stereoselective formation of 1,2-cis-glycosidic bonds is challenging. However, 1,2-cis-selectivity can be induced by remote participation of C4 or C6 ester groups. Reactions involving remote participation are believed to proceed via a key ionic intermediate, the glycosyl cation. Although mechanistic pathways were postulated many years ago, the structure of the reaction intermediates remained elusive owing to their short-lived nature. Herein, we unravel the structure of glycosyl cations involved in remote participation reactions via cryogenic vibrational spectroscopy and first principles theory. Acetyl groups at C4 ensure α-selective galactosylations by forming a covalent bond to the anomeric carbon in dioxolenium-type ions. Unexpectedly, also benzyl ether protecting groups can engage in remote participation and promote the stereoselective formation of 1,2-cis-glycosidic bonds.
RESUMO
This work presents a series of three-dimensional computational methods with the objective of analyzing and quantifying some important structural characteristics in a collection of low-density polyolefin-based foams. First, the solid phase tortuosity, local thickness, and surface curvature, have been determined over the solid phase of the foam. These parameters were used to quantify the presence of wrinkles located at the cell walls of the foams under study. In addition, a novel segmentation technique has been applied to the continuous solid phase. This novel method allows performing a separate analysis of the constituting elements of this phase, that is, cell struts and cell walls. The methodology is based on a solid classification algorithm and evaluates the local topological dissimilarities existing between these elements. Thanks to this method it was possible to perform a separate analysis of curvature, local thickness, and corrugation ratio in the solid constituents that reveals additional differences that were not detected in the first analysis of the continuous structure. The methods developed in this work are applicable to other types of porous materials in fields such as geoscience or biomedicine.