C-O Hydrogenolysis Catalyzed by Pd-PMHS Nanoparticles in the Company of Chloroarenes

被引：79

作者：

Rahaim, Ronald J., Jr. ^{[1
]}

Maleczka, Robert E., Jr. ^{[1
]}

机构：

[1] Michigan State Univ, Dept Chem, E Lansing, MI 48824 USA

来源：

ORGANIC LETTERS | 2011年 / 13卷 / 04期

关键词：

TRANSFER HYDROGENATION; PALLADIUM; POLYMETHYLHYDROSILOXANE; ALCOHOLS; OXIDATION;

D O I：

10.1021/ol102757v

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Catalytic Pd(OAc)(2) and polymethylhydrosiloxane (PMHS), in conjunction with aqueous KF, and a catalytic amount of an aromatic chloride, effects the chemo-, regio-, and stereoselective deoxygenation of benzylic oxygenated substrates at room temperature in THF. Preliminary mechanistic experiments suggest the process to involve palladium-nanoparticle-catalyzed hydrosilylation followed by C-O reduction. The chloroarene additive appears to facilitate the hydrogenolysis process through the slow controlled release of HCI.

引用

页码：584 / 587

页数：4

共 20 条

[1] Productive chloroarene C-Cl bond activation: Palladium/phosphine-catalyzed methods for oxidation of alcohols and hydrodechlorination of chloroarenes [J].

Bei, XH ;

Hagemeyer, A ;

Volpe, A ;

Saxton, R ;

Turner, H ;

Guram, AS .

JOURNAL OF ORGANIC CHEMISTRY, 2004, 69 (25) :8626-8633

[2] TRANSFER HYDROGENATION OF DIARYLACETYLENES BY POLYMETHYLHYDROSILOXANE IN THE PRESENCE OF THE RHCL3-ALIQUAT-336 CATALYST [J].

BLUM, J ;

BITAN, G ;

MARX, S ;

VOLLHARDT, KPC .

JOURNAL OF MOLECULAR CATALYSIS, 1991, 66 (03) :313-319

[3] SELECTIVE TRANSFER HYDROGENATION OF VARIOUS UNSATURATED FUNCTIONS BY POLYMETHYLHYDROSILOXANE IN THE PRESENCE OF A RECYCLABLE RHODIUM CATALYST [J].

BLUM, J ;

PRIBAR, I ;

ALPER, H .

JOURNAL OF MOLECULAR CATALYSIS, 1986, 37 (2-3) :359-367

[4] Polysiloxane-Pd nanocomposites as recyclable chemoselective hydrogenation catalysts [J].

Chauhan, BPS ;

Rathore, JS ;

Bandoo, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (27) :8493-8500

[5] Surprising role of aryl halides in nickel-catalyzed reductive aldol reactions [J].

Chrovian, Christa C. ;

Montgomery, John .

ORGANIC LETTERS, 2007, 9 (03) :537-540

[6]

Fagnou K, 2002, ANGEW CHEM INT EDIT, V41, P26, DOI 10.1002/1521-3773(20020104)41:1<26::AID-ANIE26>3.0.CO

[7]

2-9

[8] A Useful, Reliable and Safer Protocol for Hydrogenation and the Hydrogenolysis of O-Benzyl Groups: The In Situ Preparation of an Active Pd0/C Catalyst with Well-Defined Properties [J].

Felpin, Francois-Xavier ;

Fouquet, Eric .

CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (41) :12440-12445

[9] COLLOIDAL PALLADIUM, EASILY FORMED IN ORGANIC-SOLVENTS, IS A HIGHLY-ACTIVE AND STABLE CATALYST FOR SELECTIVE HYDROGENATIONS AND DEHYDROHALOGENATIONS [J].

FOWLEY, LA ;

MICHOS, D ;

LUO, XL ;

CRABTREE, RH .

TETRAHEDRON LETTERS, 1993, 34 (19) :3075-3078

[10] Productive utilization of chlorobenzene: Palladium-catalyzed selective oxidation of alcohols [J].

Guram, AS ;

Bei, XH ;

Turner, HW .

ORGANIC LETTERS, 2003, 5 (14) :2485-2487

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