PMID- 25042448 OWN - NLM STAT- PubMed-not-MEDLINE DCOM- 20150512 LR - 20140801 IS - 1521-3765 (Electronic) IS - 0947-6539 (Linking) VI - 20 IP - 32 DP - 2014 Aug 4 TI - A new class of tunable dendritic diphosphine ligands: synthesis and applications in the Ru-catalyzed asymmetric hydrogenation of functionalized ketones. PG - 9969-78 LID - 10.1002/chem.201402709 [doi] AB - A series of tunable G0-G3 dendritic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) ligands was prepared by attaching polyaryl ether dendrons onto the four phenyl rings on the P atoms. Their ruthenium complexes were employed in the asymmetric hydrogenation of beta-ketoesters, alpha-ketoesters, and alpha-ketoamides to reveal the effects of dendron size on the catalytic properties. The second- and third-generation catalysts exhibited excellent enantioselectivities, which are remarkably higher than those obtained from the small molecular catalysts and the first-generation catalyst. Molecular modeling indicates that the incorporation of bulky dendritic wedges can influence the steric environments around the metal center. In addition, the ruthenium catalyst bearing a second-generation dendritic ligand could be recycled and reused seven times without any obvious decrease in enantioselectivity. CI - (c) 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. FAU - Ma, Baode AU - Ma B AD - Beijing National Laboratory for Molecular Sciences and CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190 (P.R. China). FAU - Miao, Tingting AU - Miao T FAU - Sun, Yihua AU - Sun Y FAU - He, Yanmei AU - He Y FAU - Liu, Ji AU - Liu J FAU - Feng, Yu AU - Feng Y FAU - Chen, Hui AU - Chen H FAU - Fan, Qing-Hua AU - Fan QH LA - eng PT - Journal Article DEP - 20140710 PL - Germany TA - Chemistry JT - Chemistry (Weinheim an der Bergstrasse, Germany) JID - 9513783 OTO - NOTNLM OT - asymmetric catalysis OT - dendrimers OT - hydrogenation OT - ligands OT - ruthenium EDAT- 2014/07/22 06:00 MHDA- 2014/07/22 06:01 CRDT- 2014/07/22 06:00 PHST- 2014/03/21 00:00 [received] PHST- 2014/07/22 06:00 [entrez] PHST- 2014/07/22 06:00 [pubmed] PHST- 2014/07/22 06:01 [medline] AID - 10.1002/chem.201402709 [doi] PST - ppublish SO - Chemistry. 2014 Aug 4;20(32):9969-78. doi: 10.1002/chem.201402709. Epub 2014 Jul 10.