Highly active iridium catalysts for the hydrogenation of ketones and aldehydes

被引:49
作者
Chen, Xuanhua [1 ]
Jia, Wenli [1 ]
Guo, Rongwei [1 ]
Graham, Todd W. [1 ]
Gullons, Meredith A. [1 ]
Abdur-Rashid, Kamaluddin [1 ]
机构
[1] Kanata Chem Technol Inc, MaRS Ctr, Toronto, ON M5G 1L7, Canada
关键词
ASYMMETRIC TRANSFER HYDROGENATION; BASE-FREE CONDITIONS; STEREOSELECTIVE HYDROGENATION; ENANTIOSELECTIVE HYDROGENATION; RUTHENIUM(II) COMPLEXES; CARBONYL-COMPOUNDS; C=O HYDROGENATION; AROMATIC KETONES; HYDRIDE COMPLEX; LIGANDS;
D O I
10.1039/b815501a
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The pressure hydrogenation capabilities of the iridium pincer complexes IrH2Cl[((Pr2PC2H4)-Pr-i)(2)NH] (1) and IrH3[((Pr2PC2H4)-Pr-i)(2)NH] (2) are described and compared to related results obtained previously in transfer hydrogenation. Complex 1 was shown to act as a convenient air-stable entry point to the active catalyst 2, in the presence of base and hydrogen gas. The catalysts are active in a range of solvents, including CH2Cl2 and CHCl3, in contrast to related ruthenium systems. This class of iridium complexes is very effective for the direct hydrogenation of a wide range of carbonyl compounds including ketones, diketones, alpha,beta-unsaturated ketones and aldehydes. A catalytic cycle is proposed for this system which involves an ionic heterolytic bifunctional hydrogenation mechanism.
引用
收藏
页码:1407 / 1410
页数:4
相关论文
共 34 条
[1]   A succession of isomers of ruthenium dihydride complexes. Which one is the ketone hydrogenation catalyst? [J].
Abbel, R ;
Abdur-Rashid, K ;
Faatz, M ;
Hadzovic, A ;
Lough, AJ ;
Morris, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (06) :1870-1882
[2]   Mechanism of the hydrogenation of ketones catalyzed by trans-dihydrido(diamine)ruthenium(II) complexes [J].
Abdur-Rashid, K ;
Clapham, SE ;
Hadzovic, A ;
Harvey, JN ;
Lough, AJ ;
Morris, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (50) :15104-15118
[3]   RuHCl(diphosphine)(diamine): Catalyst precursors for the stereoselective hydrogenation of ketones and imines [J].
Abdur-Rashid, K ;
Lough, AJ ;
Morris, RH .
ORGANOMETALLICS, 2001, 20 (06) :1047-1049
[4]   Ruthenium dihydride RuH2(PPh3)2((R,R)-cyclohexyldiamine) and ruthenium monohydride RuHCl(PPh3)2((R,R)-cyclohexyldiamine):: Active catalyst and catalyst precursor for the hydrogenation of ketones and imines [J].
Abdur-Rashid, K ;
Lough, AJ ;
Morris, RH .
ORGANOMETALLICS, 2000, 19 (14) :2655-2657
[5]   Catalytic cycle for the asymmetric hydrogenation of prochiral ketones to chiral alcohols:: Direct hydride and proton transfer from chiral catalysts trans-Ru(H)2(diphosphine)(diamine) to ketones and direct addition of dihydrogen to the resulting hydridoamido complexes [J].
Abdur-Rashid, K ;
Faatz, M ;
Lough, AJ ;
Morris, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (30) :7473-7474
[6]  
Amoroso D, 2008, ALDRICHIM ACTA, V41, P15
[7]   Asymmetric transfer hydrogenation of aromatic ketones catalyzed by the iridium hydride complex under ambient conditions [J].
Chen, JS ;
Li, YY ;
Dong, ZR ;
Li, BZ ;
Gao, JX .
TETRAHEDRON LETTERS, 2004, 45 (45) :8415-8418
[8]   Mechanisms of the H2-hydrogenation and transfer hydrogenation of polar bonds catalyzed by ruthenium hydride complexes [J].
Clapham, SE ;
Hadzovic, A ;
Morris, RH .
COORDINATION CHEMISTRY REVIEWS, 2004, 248 (21-24) :2201-2237
[9]   A family of active iridium catalysts for transfer hydrogenation of ketones [J].
Clarke, Zaheer E. ;
Maragh, Paul T. ;
Dasgupta, Tara P. ;
Gusev, Dmitry G. ;
Lough, Alan J. ;
Abdur-Rashid, Kamaluddin .
ORGANOMETALLICS, 2006, 25 (17) :4113-4117
[10]   Hydrogen transfer to ketones catalyzed by Shvo's ruthenium hydride complex:: A mechanistic insight [J].
Comas-Vives, Aleix ;
Ujaque, Gregori ;
Lledos, Agusti .
ORGANOMETALLICS, 2007, 26 (17) :4135-4144