Kawabata Tomonori, Kato Masaki, Mizugaki Tomoo, Ebitani Kohki, Kaneda Kiyotomi
Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan.
Chemistry. 2004 Dec 17;11(1):288-97. doi: 10.1002/chem.200400672.
Montmorillonite-enwrapped copper and scandium catalysts (Cu(2+)- and Sc(3+)-monts) were easily prepared by treating Na(+)-mont with the aqueous solution of the copper nitrate and scandium triflate, respectively. The resulting Cu(2+)- and Sc(3+)-monts showed outstanding catalytic activities for a variety of carbon-carbon bond-forming reactions, such as the Michael reaction, the Sakurai-Hosomi allylation, and the Diels-Alder reaction, under solvent-free or aqueous conditions. The remarkable activity of the mont catalysts is attributable to the negatively charged silicate layers that are capable of stabilizing metal cations. Furthermore, these catalysts were reusable without any appreciable loss in activity and selectivity. The Cu(2+)-mont-catalyzed Michael reaction proceeds via a ternary complex in which both the 1,3-dicarbonyl compound and the enone are coordinated to a Lewis acid Cu(2+) center.
蒙脱石包裹的铜和钪催化剂(Cu(2+) - 和Sc(3+) - 蒙脱石)可通过分别用硝酸铜水溶液和三氟甲磺酸钪处理Na(+) - 蒙脱石轻松制备。所得的Cu(2+) - 和Sc(3+) - 蒙脱石在无溶剂或水相条件下,对多种碳 - 碳键形成反应表现出出色的催化活性,如迈克尔反应、樱井 - 细见烯丙基化反应和狄尔斯 - 阿尔德反应。蒙脱石催化剂的显著活性归因于能够稳定金属阳离子的带负电荷的硅酸盐层。此外,这些催化剂可重复使用,活性和选择性没有明显损失。Cu(2+) - 蒙脱石催化的迈克尔反应通过三元络合物进行,其中1,3 - 二羰基化合物和烯酮都与路易斯酸Cu(2+)中心配位。