Manganese PNP-pincer catalyzed isomerization of allylic/homo-allylic alcohols to ketones - activity, selectivity, efficiency

被引：15

作者：

Xia, Tian ^{[1
]}

Spiegelberg, Brian ^{[1
]}

Wei, Zhihong ^{[1
]}

Jiao, Haijun ^{[1
]}

Tin, Sergey ^{[1
]}

Hinze, Sandra ^{[1
]}

de Vries, Johannes G. ^{[1
]}

机构：

[1] Univ Rostock, Leibraz Inst Katalyse eV, Albert Einstein Str 29a, D-18059 Rostock, Germany

来源：

CATALYSIS SCIENCE & TECHNOLOGY | 2019年 / 9卷 / 22期

关键词：

STEREOSELECTIVE TRANSFER SEMIHYDROGENATION; ASYMMETRIC TRANSFER HYDROGENATION; ALPHA-ALKYLATION; COMPLEXES; ALKYNES; NITRILES; AMINES;

D O I：

10.1039/c9cy01502g

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：

We report the first manganese catalyzed isomerization of allylic alcohols to produce the corresponding carbonyl compounds. The ligand plays a decisive role in the efficiency of this reaction. Very high conversions could be obtained using a solvent-free reaction system. A detailed DFT study reveals a self-dehydrogenation/hydrogenation reaction mechanism which was verified by the isolation of the alpha,beta -unsaturated ketone as intermediate and a deuterium labeling experiment. It also provided a rationale for the observed selectivity and the higher efficiency of phenyl over isopropyl substitution.

引用

页码：6327 / 6334

页数：8

共 4 条

[1] Additive-Free Isomerization of Allylic Alcohols to Ketones with a Cobalt PNP Pincer Catalyst
Spiegelberg, Brian
Dell'Acqua, Andrea
Xia, Tian
Spannenberg, Anke
Tin, Sergey
Hinze, Sandra
de Vries, Johannes G.
CHEMISTRY-A EUROPEAN JOURNAL, 2019, 25 (33) : 7820 - 7825
[2] Highly Efficient Redox Isomerization of Allylic Alcohols and Transfer Hydrogenation of Ketones and Aldehydes Catalyzed by Ruthenium Complexes
Liu, Pei Nian
Ju, Kun Dong
Lau, Chak Po
ADVANCED SYNTHESIS & CATALYSIS, 2011, 353 (2-3) : 275 - 280
[3] Structure-Activity Relationship in the Iridium-Catalyzed Isomerization of Primary Allylic Alcohols
Mantilli, Luca
Gerard, David
Besnard, Celine
Mazet, Clement
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2012, (20) : 3320 - 3330
[4] One-Pot Conversion of Allylic Alcohols to α-Methyl Ketones via Iron-Catalyzed Isomerization-Methylation
Latham, Daniel E.
Polidano, Kurt
Williams, Jonathan M. J.
Morrill, Louis C.
ORGANIC LETTERS, 2019, 21 (19) : 7914 - 7918

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