SPOs as new ligands in Rh(III) catalyzed enantioselective transfer hydrogenation

被引：37

作者：

Castro, Pascal M. ^{[1
]}

Gulyas, Henrik ^{[1
,2
]}

Benet-Buchholz, Jordi ^{[1
]}

Bo, Carles ^{[1
,2
]}

Freixa, Zoraida ^{[1
]}

van Leeuwen, Piet W. N. M. ^{[1
]}

机构：

[1] Inst Chem Res Catalonia ICIQ, Tarragona 43007, Spain

[2] Univ Rovira & Virgili, Dept Quim Fis & Inorgan, Tarragona 43007, Spain

来源：

CATALYSIS SCIENCE & TECHNOLOGY | 2011年 / 1卷 / 03期

关键词：

ASYMMETRIC TRANSFER HYDROGENATION; DIPHENYLPHOSPHINOUS ACID; SECONDARY PHOSPHINE; BIDENTATE LIGANDS; RUTHENIUM HYDRIDE; RHODIUM COMPLEXES; HYDROFORMYLATION; PHOSPHORUS; OXIDE; ACTIVATION;

D O I：

10.1039/c0cy00022a

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The self-assembly of Secondary Phosphine Oxides (SPOs) into anionic bidentate chelates was used to construct unique systems for metal catalyzed transfer hydrogenation of ketones in isopropanol. Chelating bidentate or tridentate ligands were formed by assembly of secondary phosphine oxides through hydrogen bonding in the presence of rhodium trichloride as demonstrated by means of NMR spectroscopy and X-ray diffraction. When a chiral version of an SPO was used in asymmetric transfer hydrogenation of isopropanol and acetophenone, an enantiomeric excess of 89% was achieved. The presence of at least two ligands in the catalytically active species was confirmed by a positive non-linear effect. DFT calculations were applied to characterize several intermediates for the isopropanol dehydrogenation to produce a rhodium hydride complex and acetone. A transition state for the hydrogen-transfer was fully characterized, which revealed that the process occurs via a concerted outer-sphere mechanism.

引用

页码：401 / 407

页数：7

共 56 条

[1] Air- and moisture-stable secondary phosphine oxides as preligands in catalysis [J].

Ackermann, Lutz .

SYNTHESIS-STUTTGART, 2006, 10 (10) :1557-1571

[2] Air-Stable Secondary Phosphine Oxide as Preligand for Palladium-Catalyzed Intramolecular α-Arylations with Chloroarenes [J].

Ackermann, Lutz ;

Vicente, Ruben ;

Hofmann, Nora .

ORGANIC LETTERS, 2009, 11 (19) :4274-4276

[3] H-TRANSFER CATALYSIS WITH RU3(CO)12 [J].

BLUM, Y ;

RESHEF, D ;

SHVO, Y .

TETRAHEDRON LETTERS, 1981, 22 (16) :1541-1544

[4] Supramolecular approaches to generate libraries of chelating bidentate ligands for homogeneous catalysis [J].

Breit, B .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (42) :6816-6825

[5]

BREIT B, 2008, SUPRAMOLECULAR CATAL, P29

[6] Intramolecular trapping of an intermediate in the reduction of Imines by a hydroxycyclopentadienyl ruthenium hydride: Support for a concerted outer sphere mechanism [J].

Casey, Charles P. ;

Clark, Timothy B. ;

Guzei, Ilia A. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (38) :11821-11827

[7] Hydrogen elimination from a hydroxycyclopentadienyl ruthenium(II) hydride: Study of hydrogen activation in a ligand-metal bifunctional hydrogenation catalyst [J].

Casey, CP ;

Johnson, JB ;

Singer, SW ;

Cui, Q .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (09) :3100-3109

[8] HYDROLYSIS OF MONOCHLOROPHOSPHINE AND MONOCHLOROARSINE COMPLEXES OF PLATINUM(2) - BRIDGING PHOSPHINATO- AND ARSINATO-GROUPS [J].

CHATT, J ;

HEATON, BT .

JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1968, (11) :2745-&

[9] A theoretical study of X ligand effect on catalytic activity of complexes RuHX(diamine)(PPh3)2 (X = NCMe, CO, Cl, OMe, OPh, CCMe and H) in H2-hydrogenation of ketones [J].

Chen, Zhuo ;

Chen, Yue ;

Tang, Yanhui ;

Lei, Ming .

DALTON TRANSACTIONS, 2010, 39 (08) :2036-2043

[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

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