Ruthenium-Catalyzed Selective Hydrogenation of Epoxides to Secondary Alcohols

被引：30

作者：

Thiyagarajan, Subramanian ^{[1
]}

Gunanathan, Chidambaram ^{[1
]}

机构：

[1] HBNI, Natl Inst Sci Educ & Res, Sch Chem Sci, Bhubaneswar 752050, Odisha, India

来源：

ORGANIC LETTERS | 2019年 / 21卷 / 23期

关键词：

LITHIUM ALUMINUM-HYDRIDE; TERMINAL EPOXIDES; CHEMOSELECTIVE HYDROGENOLYSIS; REGIOSELECTIVE REDUCTION; OXIDATION; HYDROSILYLATION; ISOMERIZATION; OLEFINS; SYSTEM; ACID;

D O I：

10.1021/acs.orglett.9b03995

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A ruthenium(II)-catalyzed highly selective Markovnikov hydrogenation of terminal epoxides to secondary alcohols is reported. Diverse substitutions on the aryl ring of styrene oxides are tolerated. Benzylic, glycidyl, and aliphatic epoxides as well as diepoxides also underwent facile hydrogenation to provide secondary alcohols with exclusive selectivity. Metal-ligand cooperation-mediated ruthenium trans-dihydride formation and its reaction involving oxygen and the less substituted terminal carbon of the epoxide is envisaged for the origin of the observed selectivity.

引用

页码：9774 / 9778

页数：5

共 51 条

[1] Study of Precatalyst Degradation Leading to the Discovery of a New Ru0 Precatalyst for Hydrogenation and Dehydrogenation [J].

Anaby, Aviel ;

Schelwies, Mathias ;

Schwaben, Jonas ;

Rominger, Frank ;

Hashmi, A. Stephen K. ;

Schaub, Thomas .

ORGANOMETALLICS, 2018, 37 (13) :2193-2201

[2] The ruthenium-catalysed selective synthesis of mono-deuterated terminal alkynes [J].

Chatterjee, Basujit ;

Gunanathan, Chidambaram .

CHEMICAL COMMUNICATIONS, 2016, 52 (24) :4509-4512

[3] Ruthenium Catalyzed Selective α- and α,β-Deuteration of Alcohols Using D2O [J].

Chatterjee, Basujit ;

Gunanathan, Chidambaram .

ORGANIC LETTERS, 2015, 17 (19) :4794-4797

[4] Recent progress in Wacker oxidations: Moving toward molecular oxygen as the sole oxidant [J].

Cornell, Candace N. ;

Sigman, Matthew S. .

INORGANIC CHEMISTRY, 2007, 46 (06) :1903-1909

[5]

Cr W, 2017, J NANOMATER MOL NANO, V6, P2, DOI DOI 10.3998/ERG0.12405314.0002.008

[6] Catalytic Functionalization of Styrenyl Epoxides via 2-Nickela(II)oxetanes [J].

Desnoyer, Addison N. ;

Geng, Jialing ;

Drover, Marcus W. ;

Patrick, Brian O. ;

Love, Jennifer A. .

CHEMISTRY-A EUROPEAN JOURNAL, 2017, 23 (48) :11509-11512

[7] PALLADIUM-CATALYZED, REGIOSELECTIVE REDUCTION OF 1,2-EPOXIDES BY AMMONIUM FORMATE [J].

DRAGOVICH, PS ;

PRINS, TJ ;

ZHOU, R .

JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (15) :4922-4924

[8]

Eckert M, 2000, ULLMANNS ENCY IND CH, V1, P191

[9]

FUJITSU H, 1981, J ORG CHEM, V46, P2287, DOI 10.1021/jo00324a016

[10] Highly Active Titanocene Catalysts for Epoxide Hydrosilylation: Synthesis, Theory, Kinetics, EPR Spectroscopy [J].

Henriques, Dina Schwarz G. ;

Zimmer, Katharina ;

Klare, Sven ;

Meyer, Andreas ;

Rojo-Wiechel, Elena ;

Bauer, Mirko ;

Sure, Rebecca ;

Grimme, Stefan ;

Schiemann, Olav ;

Flowers, Robert A., II ;

Gansaeuer, Andreas .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (27) :7671-7675

← 1 2 3 4 5 6 →