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.

引用

页码：6467 / 6470

页数：4

共 64 条

[31] Strategies for nucleophilic, electrophilic, and radical trifluoromethylations [J].

Ma, Jun-An ;

Cahard, Dominique .

JOURNAL OF FLUORINE CHEMISTRY, 2007, 128 (09) :975-996

[32] Update 1 of: Asymmetric Fluorination, Trifluoromethylation, and Perfluoroalkylation Reactions [J].

Ma, Jun-An ;

Cahard, Dominique .

CHEMICAL REVIEWS, 2008, 108 (09) :PR1-PR43

[33] Platinum Metals in the Catalytic Asymmetric Isomerization of Allylic Alcohols [J].

Mantilli, Luca ;

Mazet, Clement .

CHEMISTRY LETTERS, 2011, 40 (04) :341-344

[34] Improved Catalysts for the Iridium-Catalyzed Asymmetric Isomerization of Primary Allylic Alcohols Based on Charton Analysis [J].

Mantilli, Luca ;

Gerard, David ;

Torche, Sonya ;

Besnard, Celine ;

Mazet, Clement .

CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (42) :12736-12745

[35] Expanded scope for the iridium-catalyzed asymmetric isomerization of primary allylic alcohols using readily accessible second-generation catalysts [J].

Mantilli, Luca ;

Mazet, Clement .

CHEMICAL COMMUNICATIONS, 2010, 46 (03) :445-447

[36] Highly efficient redox isomerization of allylic alcohols at ambient temperature catalyzed by novel ruthenium-cyclopentadienyl complexes-new insight into the mechanism [J].

Martín-Matute, B ;

Bogár, K ;

Edin, M ;

Kaynak, FB ;

Bäckvall, JE .

CHEMISTRY-A EUROPEAN JOURNAL, 2005, 11 (20) :5832-5842

[37] Synthesis of α-CF3-Substituted Carbonyl Compounds with Relative and Absolute Stereocontrol Using Electrophilic CF3-Transfer Reagents [J].

Matousek, Vaclav ;

Togni, Antonio ;

Bizet, Vincent ;

Cahard, Dominique .

ORGANIC LETTERS, 2011, 13 (21) :5762-5765

[38] Enantioselective α-Trifluoromethylation of Aldehydes via Photoredox Organocatalysis [J].

Nagib, David A. ;

Scott, Mark E. ;

MacMillan, David W. C. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (31) :10875-+

[39] Asymmetric Construction of Stereogenic Carbon Centers Featuring a Trifluoromethyl Group from Prochiral Trifluoromethylated Substrates [J].

Nie, Jing ;

Guo, Hong-Chao ;

Cahard, Dominique ;

Ma, Jun-An .

CHEMICAL REVIEWS, 2011, 111 (02) :455-529

[40] trans-RuH(η1-BH4)(binap)(1,2-diamine):: a catalyst for asymmetric hydrogenation of simple ketones under base-free conditions [J].

Ohkuma, T ;

Koizumi, M ;

Muñiz, K ;

Hilt, G ;

Kabuto, C ;

Noyori, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (23) :6508-6509

← 1 2 3 4 5 6 7 →