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.
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收藏
页码：6327 / 6334
页数：8
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  • [1] Catalytic Formal Hydroamination of Allylic Alcohols Using Manganese PNP-Pincer Complexes
    Duarte de Almeida, Leandro
    Bourriquen, Florian
    Junge, Kathrin
    Beller, Matthias
    [J]. ADVANCED SYNTHESIS & CATALYSIS, 2021, 363 (17) : 4177 - 4181
  • [2] Isomerization of Allylic Alcohols to Ketones Catalyzed by Well-Defined Iron PNP Pincer Catalysts
    Xia, Tian
    Wei, Zhihong
    Spiegelberg, Brian
    Jiao, Haijun
    Hinze, Sandra
    de Vries, Johannes G.
    [J]. CHEMISTRY-A EUROPEAN JOURNAL, 2018, 24 (16) : 4043 - 4049
  • [3] 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.
    [J]. CHEMISTRY-A EUROPEAN JOURNAL, 2019, 25 (33) : 7820 - 7825
  • [4] RUTHENIUM-CATALYZED ISOMERIZATION OF ALLYLIC ALCOHOLS TO SATURATED KETONES
    BACKVALL, JE
    ANDREASSON, U
    [J]. TETRAHEDRON LETTERS, 1993, 34 (34) : 5459 - 5462
  • [5] Synthesis of β-CF3 ketones from trifluoromethylated allylic alcohols by ruthenium catalyzed isomerization
    Bizet, Vincent
    Pannecoucke, Xavier
    Renaud, Jean-Luc
    Cahard, Dominique
    [J]. JOURNAL OF FLUORINE CHEMISTRY, 2013, 152 : 56 - 61
  • [6] Chromium catalyzed oxidation of (homo-)allylic and (homo-)propargylic alcohols with sodium periodate to ketones or carboxylic acids
    Schmieder-van de Vondervoort, L
    Bouttemy, S
    Padrón, JM
    Le Bras, J
    Muzart, J
    Alsters, PL
    [J]. SYNLETT, 2002, (02) : 243 - 246
  • [7] Palladium-catalyzed isomerization of (homo-)allylic alcohols in molten tetrabutylammonium bromide, a recyclable system
    Ganchegui, B
    Bouquillon, S
    Hénin, F
    Muzart, J
    [J]. JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2004, 214 (01) : 65 - 69
  • [8] 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
    [J]. ADVANCED SYNTHESIS & CATALYSIS, 2011, 353 (2-3) : 275 - 280
  • [9] Structure-Activity Relationship in the Iridium-Catalyzed Isomerization of Primary Allylic Alcohols
    Mantilli, Luca
    Gerard, David
    Besnard, Celine
    Mazet, Clement
    [J]. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2012, (20) : 3320 - 3330
  • [10] RUCL3, NAOH-CATALYZED ISOMERIZATION OF ALLYLIC ALCOHOLS TO SATURATED KETONES .2. REGIOCHEMISTRY
    SMADJA, W
    VALERY, JM
    VILLE, G
    BERNASSAU, JM
    [J]. JOURNAL OF MOLECULAR CATALYSIS, 1985, 30 (03): : 389 - 394
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