Iridium-catalyzed efficient reduction of ketones in water with formic acid as a hydride donor at low catalyst loading

被引：68

作者：

Liu, Ji-tian ^{[1
,2
]}

Yang, Shiyi ^{[2
]}

Tang, Weiping ^{[3
]}

Yang, Zhanhui ^{[2
]}

Xu, Jiaxi ^{[2
]}

机构：

[1] Peking Univ, Coll Chem & Mol Engn, Beijing 100871, Peoples R China

[2] Beijing Univ Chem Technol, Dept Organ Chem, State Key Lab Chem Resource Engn, Fac Sci, Beijing 100029, Peoples R China

[3] Univ Wisconsin, Sch Pharm, Madison, WI 53705 USA

来源：

GREEN CHEMISTRY | 2018年 / 20卷 / 09期

基金：

中国国家自然科学基金; 中国博士后科学基金;

关键词：

ASYMMETRIC TRANSFER HYDROGENATION; SOLUBLE AMINOSULFONAMIDE LIGANDS; DEPENDENT TRANSFER HYDROGENATION; BIPHASIC TRANSFER HYDROGENATION; AQUEOUS SODIUM FORMATE; ASTERISK-IR COMPLEXES; CARBONYL-COMPOUNDS; GREEN CHEMISTRY; CP-ASTERISK; RHODIUM COMPLEXES;

D O I：

10.1039/c8gc00348c

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A highly efficient and chemoselective transfer hydrogenation of ketones in water has been successfully achieved with our newly developed catalyst. Simple ketones, as well as - or -functionalized ketones, are readily reduced. Formic acid is used as a traceless hydride source. At very low catalyst loading (S/C = 10000 in most cases; S/C = 50000 or 100000 in some cases), the iridium catalyst is impressively efficient at reducing ketones in good to excellent yields. The TOF value can be as high as up to 26000 mol mol(-1) h(-1). A variety of functional groups are well tolerated, for example, heteroaryl, aryloxy, alkyloxy, halogen, cyano, nitro, ester, especially acidic methylene, phenol and carboxylic acid groups.

引用

页码：2118 / 2124

页数：7

共 63 条

[1] Isolation and crystal structure of a water-soluble iridium hydride: A robust and highly active catalyst for acid-catalyzed transfer hydrogenations of carbonyl compounds in acidic media [J].

Abura, T ;

Ogo, S ;

Watanabe, Y ;

Fukuzumi, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (14) :4149-4154

[2] The biphasic transfer hydrogenation of aldehydes and ketones with isopropanol catalyzed by water-soluble rhodium complexes [J].

Ajjou, AN ;

Pinet, JL .

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2004, 214 (02) :203-206

[3] Green chemistry tools to influence a medicinal chemistry and research chemistry based organisation [J].

Alfonsi, Kim ;

Colberg, Juan ;

Dunn, Peter J. ;

Fevig, Thomas ;

Jennings, Sandra ;

Johnson, Timothy A. ;

Kleine, H. Peter ;

Knight, Craig ;

Nagy, Mark A. ;

Perry, David A. ;

Stefaniak, Mark .

GREEN CHEMISTRY, 2008, 10 (01) :31-36

[4] pH-Independent Transfer Hydrogenation in Water: Catalytic, Enantioselective Reduction of β-Keto Esters [J].

Ariger, Martin A. ;

Carreira, Erick M. .

ORGANIC LETTERS, 2012, 14 (17) :4522-4524

[5] Transition metal hydrides as active intermediates in hydrogen transfer reactions [J].

Bäckvall, JE .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2002, 652 (1-2) :105-111

[6] TRANSITION METAL-CATALYZED TRANSFER REDUCTION OF SATURATED ALDEHYDES AND KETONES BY SODIUM FORMATE UNDER PHASE-TRANSFER CONDITIONS [J].

BAR, R ;

SASSON, Y ;

BLUM, J .

JOURNAL OF MOLECULAR CATALYSIS, 1984, 26 (03) :327-332

[7] PHASE TRANSFER-CATALYZED REDUCTION OF AROMATIC-ALDEHYDES BY AQUEOUS SODIUM FORMATE IN THE PRESENCE OF DICHLOROTRIS(TRIPHENYLPHOSPHINE)RUTHENIUM(II) - A KINETIC-STUDY [J].

BAR, R ;

BAR, LK ;

SASSON, Y ;

BLUM, J .

JOURNAL OF MOLECULAR CATALYSIS, 1985, 33 (02) :161-177

[8] 1-(pyridin-2-yl)methanamine-based ruthenium catalysts for fast transfer hydrogenation of carbonyl compounds in 2-propanol [J].

Baratta, Walter ;

Rigo, Pierluigi .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2008, (26) :4041-4053

[9] Long-range metal-ligand bifunctional catalysis: cyclometallated iridium catalysts for the mild and rapid dehydrogenation of formic acid [J].

Barnard, Jonathan H. ;

Wang, Chao ;

Berry, Neil G. ;

Xiao, Jianliang .

CHEMICAL SCIENCE, 2013, 4 (03) :1234-1244

[10] Enantioselective Synthesis of Alcohols and Amines by Iridium-Catalyzed Hydrogenation, Transfer Hydrogenation, and Related Processes [J].

Bartoszewicz, Agnieszka ;

Ahlsten, Nanna ;

Martin-Matute, Belen .

CHEMISTRY-A EUROPEAN JOURNAL, 2013, 19 (23) :7274-7302

← 1 2 3 4 5 6 7 →