Yasukawa Tomohiro, Miyamura Hiroyuki, Kobayashi Shū
Department of Chemistry , School of Science , The University of Tokyo , Hongo, Bunkyo-ku , Tokyo 113-0033 , Japan . Email:
Chem Sci. 2015 Nov 1;6(11):6224-6229. doi: 10.1039/c5sc02510a. Epub 2015 Aug 12.
Cellulose-supported chiral Rh nanoparticle (NP) catalysts have been developed. The Rh NPs, which were well dispersed on cellulose, catalyzed the asymmetric 1,4-addition of arylboronic acids to enones and enoates, one of the representative asymmetric carbon-carbon bond-forming reactions, in the presence of chiral diene ligands, providing the corresponding adducts in high yields with outstanding enantioselectivities without metal leaching. The solid-state NMR analysis of the chiral NP system directly suggested interactions between the Rh NPs and the chiral ligand on cellulose. This is the first example of using polysaccharide-supported chiral metal nanoparticles for asymmetric carbon-carbon bond-forming reactions.
纤维素负载的手性铑纳米颗粒（NP）催化剂已被开发出来。铑纳米颗粒均匀分散在纤维素上，在手性二烯配体存在的情况下，催化芳基硼酸与烯酮和烯酸酯的不对称1,4-加成反应，这是一种典型的不对称碳-碳键形成反应，能以高产率和出色的对映选择性提供相应的加合物，且无金属浸出。对手性纳米颗粒体系的固态核磁共振分析直接表明了铑纳米颗粒与纤维素上手性配体之间的相互作用。这是多糖负载的手性金属纳米颗粒用于不对称碳-碳键形成反应的首个实例。
