Hydrogen-Bonding 3D Networks by Polyhedral Organosilanols: Selective Inclusion of Hydrocarbons in Open Frameworks
摘要:
Tetrahedral organosilanols E[C6H4Si(i-Pr)(2)OH](4) (E = C, 2a, E = Si, 2b) as well as octahedral organosilanols Si8O12(CH=CHC6H4SiR2OH)(8) (R =i-Pr, 5a; R = Ph, 5b) have been derived from tetraphenylmethane and lane (1a,b) and octavinyloctasilsesquioxane (3) designed for self-assembly of 3D hydrogen-bonding networks possessing large porosity. X-ray analyses following crystallization of 2a,b from THF/benzene and either hexane or heptane revealed adamantane-type networks with hydrogen bonds between the silanols of four separate molecules and selective inclusion of hexane or heptane, respectively Upon changing the mixed solvent to THF/benzene/cyclohexane, X-ray analysis of 2a showed an inclusion compound of composition 2a.1.5benzene TOPOS analyses of 2a.1.5benzene demonstrated a non-adamantane-type framework with sra network topology Crystallization of 5a.b from acetone/benzene followed by X-ray analyses confirmed the production of the inclusion compounds 5a.18benzene and 5b.23benzene. The open frameworks of 5a.18benzene and 5b.23benzene are constructed with zeolitic or fluorite cages, and ast or flu network topology results, based on the TOPOS program The packing of benzene molecules in 5a.18benzene and 5b.23benzenc was found to be similar to that of crystals of pure benzene in edge-to-face arrangements. Thus, hydrogen-bonding networks of polyhedral organosilanols have shown selective inclusion of hydrocarbons into large cavities with adjustable porosity and without interpenetration of one network into another
Hydrogen-Bonding 3D Networks by Polyhedral Organosilanols: Selective Inclusion of Hydrocarbons in Open Frameworks
摘要:
Tetrahedral organosilanols E[C6H4Si(i-Pr)(2)OH](4) (E = C, 2a, E = Si, 2b) as well as octahedral organosilanols Si8O12(CH=CHC6H4SiR2OH)(8) (R =i-Pr, 5a; R = Ph, 5b) have been derived from tetraphenylmethane and lane (1a,b) and octavinyloctasilsesquioxane (3) designed for self-assembly of 3D hydrogen-bonding networks possessing large porosity. X-ray analyses following crystallization of 2a,b from THF/benzene and either hexane or heptane revealed adamantane-type networks with hydrogen bonds between the silanols of four separate molecules and selective inclusion of hexane or heptane, respectively Upon changing the mixed solvent to THF/benzene/cyclohexane, X-ray analysis of 2a showed an inclusion compound of composition 2a.1.5benzene TOPOS analyses of 2a.1.5benzene demonstrated a non-adamantane-type framework with sra network topology Crystallization of 5a.b from acetone/benzene followed by X-ray analyses confirmed the production of the inclusion compounds 5a.18benzene and 5b.23benzene. The open frameworks of 5a.18benzene and 5b.23benzene are constructed with zeolitic or fluorite cages, and ast or flu network topology results, based on the TOPOS program The packing of benzene molecules in 5a.18benzene and 5b.23benzenc was found to be similar to that of crystals of pure benzene in edge-to-face arrangements. Thus, hydrogen-bonding networks of polyhedral organosilanols have shown selective inclusion of hydrocarbons into large cavities with adjustable porosity and without interpenetration of one network into another
Polystyrene-Supported Triphenylsilyl Chloride for the Silylation-Based Kinetic Resolution of Secondary Alcohols
作者:Ravish K. Akhani、Robert W. Clark、Liang Yuan、Li Wang、Chuanbing Tang、Sheryl L. Wiskur
DOI:10.1002/cctc.201500173
日期:2015.5.18
A silyl chloride derivatized styrene polymer was employed in the silylation‐based kineticresolution of secondaryalcohols for chromatography‐free separation of alcohol enantiomers. Synthetically useful selectivity factors were obtained; furthermore, the polymer was recycled for use in a subsequent kineticresolution, and it maintained its selectivity and integrity.