文献类型：期刊文献

英文题名：Synthesis of iridium and rhodium complexes with new chiral phosphine-NHC ligands based on 1,1′-binaphthyl framework and their application in asymmetric hydrogenation

作者：Gu, Peng[1,2];Zhang, Jun[1,2];Xu, Qin[1,2];Shi, Min[1,2,3]

机构：[1]E China Univ Sci & Technol, Key Lab Adv Mat, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[2]E China Univ Sci & Technol, Inst Fine Chem, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[3]Chinese Acad Sci, State Key Lab Organometall Chem, Shanghai Inst Organ Chem, Shanghai 200032, Peoples R China

年份：2013

卷号：42

期号：37

起止页码：13599

外文期刊名：DALTON TRANSACTIONS

收录：;EI(收录号：20133716734698);WOS:【SCI-EXPANDED(收录号:WOS:000323759600041)】；

基金：We thank the Shanghai Municipal Committee of Science and Technology (11JC1402600), the National Basic Research Program of China (973)-2010CB833302, the Fundamental Research Funds for the Central Universities, and the National Natural Science Foundation of China for financial support (21072206, 20472096, 20872162, 20672127, 21121062 and 20732008).

语种：英文

外文关键词：Chelation - Synthesis (chemical) - Organic compounds - X ray diffraction analysis - Iridium compounds - Rhodium compounds - Hydrogenation - Phosphorus compounds

摘要：The first series of chiral phosphine-imidazole carbene ligands based on a 1,1'-binaphthyl framework were synthesized from (R)-2-amine-2'-(diphenylphosphino)-1,1'-binaphthyl (1) in a four-step pathway. After deprotonation of these phosphine-imidazolium salts with (LiOBu)-Bu-t, and subsequent complexation with [Ir(COD)Cl](2) and anion exchange with NaBArF, phosphine-carbene chelated iridium complexes (R)-6a and (R)-6b were obtained. Their structures have been characterized by NMR and X-ray diffraction analysis. The NHC-phosphine rhodium complex (R)-6c has been also obtained by a similar synthetic method. These iridium complexes have been applied to catalyze the asymmetric hydrogenation of alkenes to give the corresponding products in moderate to excellent conversion (up to 99%) and moderate enantioselectivities under mild conditions (up to 61% ee).