The effectiveness of cationic species for increasing the catalytic activity of organotin Lewis acids has been assessed by comparing two types of cationic organotin clusters, [Bu2Sn(OH)-(H2O)](2)(2+)2OTf(-) and [(BuSn)(12)O-14(OH)(6)]Cl-2+(2)-.2H(2)O, with neutral clusters in alcohol acetylation. The Sn-2 dication is extremely active, with a catalyst concentration of 0.001 mol %, sufficient to give a quantitative yield. The Sn-12 dication is slightly less active but gives high levels of chemoselectivity and primary/secondary alcohols selection. The neutral clusters are less effective catalysts. A variety of synthetic applications are feasible by changing the Lewis acidity of the catalysts.
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