Ruthenium-Catalyzed Deuteration of Alcohols with Deuterium Oxide

被引：41

作者：

Bai, Wei ^{[1
]}

Lee, Ka-Ho ^{[1
]}

Tse, Sunny Kai San ^{[1
]}

Chan, Ka Wing ^{[1
]}

Lin, Zhenyang ^{[1
]}

Jia, Guochen ^{[1
]}

机构：

[1] Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong, Peoples R China

来源：

ORGANOMETALLICS | 2015年 / 34卷 / 15期

关键词：

D EXCHANGE-REACTION; ASYMMETRIC TRANSFER HYDROGENATION; LIGAND BIFUNCTIONAL CATALYSIS; EFFECTIVE CORE POTENTIALS; SELECTIVE H/D EXCHANGE; H BOND ACTIVATION; AB-INITIO; REGIOSELECTIVE DEUTERATION; AQUEOUS-SOLUTION; MOLECULAR CALCULATIONS;

D O I：

10.1021/acs.organomet.5b00134

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The catalytic properties of a series of ruthenium complexes for H/D exchange between D2O and alcohols were studied. The catalytic activity of the ruthenium complexes and the regioselectivity of the H/D exchange reactions were found to be dependent on the auxiliary ligands. While ruthenium eta(6)-cymene complexes such as cymene)RuCl(NH2CH2CH2NTs)]Cl, (eta(6)-cymene)RuCl2/ NH2CH2CH2OH, and (eta(6)-cymene)Ru{(S,S)-NHCHPhCHPhNTs} catalyzed regioselective deuteration of alcohols with D2O at the beta-carbon positions only, octahedral ruthenium complexes such as RuCl2(2-NH2CH2Py)(PPh3)(2) (2-NH2CH2Py = 2-aminomethylpyridine) and RuCl2(NH2CH2CH2NH2)(PPh3)(2) catalyzed regioselective H/D exchange reactions of D2O with alcohols at both the alpha- and beta-carbon positions of alcohols. The H/D exchange reactions proceed through reversible dehydrogenation of alcohols and hydrogenation of carbonyl compounds involving hydride species and H/D exchange among D2O and carbonyl and hydride species. The different regioselectivities of the H/D exchange reactions can be related to the relative ease of H/D exchange of ruthenium hydride intermediates with D2O.

引用

页码：3686 / 3698

页数：13

共 116 条

[1] Chemistry of ruthenium(II) monohydride and dihydride complexes containing pyridyl donor ligands including catalytic ketone H2-hydrogenation [J].

Abdur-Rashid, K ;

Abbel, R ;

Hadzovic, A ;

Lough, AJ ;

Morris, RH .

INORGANIC CHEMISTRY, 2005, 44 (07) :2483-2492

[2] 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

[3]

Adad J.L., 2004, J. Org. Chem, V69, P7108

[4]

Ahmad N., 1974, INORG SYNTH, V15, P48

[5] Arene Ruthenium Complexes as Versatile Catalysts in Water in both Transfer Hydrogenation of Ketones and Oxidation of Alcohols. Selective Deuterium Labeling of rac-1-Phenylethanol [J].

Aliende, Cristina ;

Perez-Manrique, Mercedes ;

Jalon, Felix A. ;

Manzano, Blanca R. ;

Rodriguez, Ana M. ;

Espino, Gustavo .

ORGANOMETALLICS, 2012, 31 (17) :6106-6123

[6] Regio- and stereoselective deuteration of allylic chlorides controlled by neighboring alcohol or ether groups [J].

Andersson, PG .

JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (12) :4154-4156

[7] Relative Gibbs energies in solution through continuum models:: Effect of the loss of translational degrees of freedom in bimolecular reactions on Gibbs energy barriers [J].

Ardura, D ;

López, R ;

Sordo, TL .

JOURNAL OF PHYSICAL CHEMISTRY B, 2005, 109 (49) :23618-23623

[8] Theoretical Investigation into the Mechanism of 3′-dGMP Oxidation by [PtIVCl4(dach)] [J].

Ariafard, Alireza ;

Ghohe, Narges Mandizadeh ;

Abbasi, Kiana Khadem ;

Canty, Allan J. ;

Yates, Brian F. .

INORGANIC CHEMISTRY, 2013, 52 (02) :707-717

[9] DFT Study on the Mechanism of the Activation and Cleavage of CO2 by (NHC)CuEPh3 (E = Si, Ge, Sn) [J].

Ariafard, Alireza ;

Brookes, Nigel J. ;

Stranger, Robert ;

Yates, Brian F. .

ORGANOMETALLICS, 2011, 30 (06) :1340-1349

[10] Facile scission of isonitrile carbon-nitrogen triple bond using a diborane(4) reagent [J].

Asakawa, Hiroki ;

Lee, Ka-Ho ;

Lin, Zhenyang ;

Yamashita, Makoto .

NATURE COMMUNICATIONS, 2014, 5

← 1 2 3 4 5 6 7 8 9 10 →