Ruthenium-Catalyzed Redox Isomerization of Trifluoromethylated Allylic Alcohols: Mechanistic Evidence for an Enantiospecific Pathway

被引：92
作者：
Bizet, Vincent [1 ]
Pannecoucke, Xavier [1 ]
Renaud, Jean-Luc [2 ]
Cahard, Dominique [1 ]
机构：
[1] Univ & INSA Rouen, COBRA, UMR CNRS 6014, F-76821 Mont St Aignan, France
[2] Univ Caen ENSICAEN, LCMT, UMR CNRS 6507, F-14050 Caen, France
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2012年 / 51卷 / 26期
关键词：
asymmetric catalysis; fluorine; isomerization; redox chemistry; ruthenium; ENANTIOSELECTIVE ALPHA-TRIFLUOROMETHYLATION; ASYMMETRIC TRANSFER HYDROGENATION; CARBONYL-COMPOUNDS; STEREOSELECTIVE-SYNTHESIS; MICHAEL ADDITION; PROPARGYLIC ALCOHOLS; CONJUGATE REDUCTION; EFFICIENT CATALYST; KETONES; COMPLEXES;
D O I：
10.1002/anie.201200827
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Transfer news: A synthetic approach to chiral β-CF 3- substituted saturated carbonyl compounds has been developed in which ruthenium complexes efficiently catalyze the redox isomerization of CF 3-bearing allylic alcohols by an intramolecular suprafacial enantiospecific 1,3-hydrogen transfer (see scheme). This method was used for the enantioselective synthesis of (S)-CF 3-citronellol. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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页码：6467 / 6470
页数：4
相关论文
共 64 条
[1]   Allylic alcohols as synthetic enolate equivalents: Isomerisation and tandem reactions catalysed by transition metal complexes [J].
Ahlsten, Nanna ;
Bartoszewicz, Agnieszka ;
Martin-Matute, Belen .
DALTON TRANSACTIONS, 2012, 41 (06) :1660-1670
[2]   A Facile Synthesis of α-Fluoro Ketones Catalyzed by [Cp*IrCl2]2 [J].
Ahlsten, Nanna ;
Bartoszewicz, Agnieszka ;
Agrawal, Santosh ;
Martin-Matute, Belen .
SYNTHESIS-STUTTGART, 2011, (16) :2600-2608
[3]   Ir-catalysed formation of C-F bonds. From allylic alcohols to α-fluoroketones [J].
Ahlsten, Nanna ;
Martin-Matute, Belen .
CHEMICAL COMMUNICATIONS, 2011, 47 (29) :8331-8333
[4]   Rhodium-catalysed isomerisation of allylic alcohols in water at ambient temperature [J].
Ahlsten, Nanna ;
Lundberg, Helena ;
Martin-Matute, Belen .
GREEN CHEMISTRY, 2010, 12 (09) :1628-1633
[5]   Practical Enantioselective Synthesis of a 3-Aryl-3-trifluoromethyl-2-aminopropanol Derivative [J].
Alimardanov, Asaf ;
Nikitenko, Antonia ;
Connolly, Terrence J. ;
Feigelson, Gregg ;
Chan, Anita W. ;
Ding, Zhixian ;
Ghosh, Mousumi ;
Shi, Xinxu ;
Ren, Jianxin ;
Hansen, Eric ;
Farr, Roger ;
MacEwan, Michael ;
Tadayon, Sam ;
Springer, Dane M. ;
Kreft, Anthony F. ;
Ho, Douglas M. ;
Potoski, John R. .
ORGANIC PROCESS RESEARCH & DEVELOPMENT, 2009, 13 (06) :1161-1168
[6]   The Productive Merger of Iodonium Salts and Organocatalysis: A Non-photolytic Approach to the Enantioselective α-Trifluoromethylation of Aldehydes [J].
Allen, Anna E. ;
MacMillan, David W. C. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (14) :4986-+
[7]   Evidence for a ruthenium dihydride species as the active catalyst in the RuCl2(PPh3)-catalyzed hydrogen transfer reaction in the presence of base [J].
Aranyos, A ;
Csjernyik, G ;
Szabó, KJ ;
Bäckvall, JE .
CHEMICAL COMMUNICATIONS, 1999, (04) :351-352
[8]   Enantioselective Synthesis of β-Trifluoromethyl α-Amino Acids [J].
Benhaim, Cyril ;
Bouchard, Luc ;
Pelletier, Guillaume ;
Sellstedt, John ;
Kristofova, Livia ;
Daigneault, Sylvain .
ORGANIC LETTERS, 2010, 12 (09) :2008-2011
[9]   Pentamethylcyclopentadienyl ruthenium: an efficient catalyst for the redox isomerization of functionalized allylic alcohols into carbonyl compounds [J].
Bouziane, Asmae ;
Carboni, Bertrand ;
Bruneau, Christian ;
Carreaux, Francois ;
Renaud, Jean-Luc .
TETRAHEDRON, 2008, 64 (51) :11745-11750
[10]   Bis(allyl)-ruthenium(IV) complexes as highly efficient catalysts for the redox isomerization of allylic alcohols into carbonyl compounds in organic and aqueous media:: Scope, limitations, and theoretical analysis of the mechanism [J].
Cadierno, V ;
García-Garrido, SE ;
Gimeno, J ;
Varela-Alvarez, A ;
Sordo, JA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (04) :1360-1370
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