Palladium-Catalyzed Cascade CH Trifluoroethylation of Aryl Iodides and Heck Reaction: Efficient Synthesis of ortho-Trifluoroethylstyrenes

A palladium‐catalyzed selective CH bond trifluoroethylation of aryl iodides has been explored. The reaction allows for the efficient synthesis of a variety of ortho‐trifluoroethyl‐substituted styrenes. Preliminary mechanistic studies indicate that the reaction might involve a key PdIV intermediate,...

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Published inAngewandte Chemie (International ed.) Vol. 53; no. 38; pp. 10174 - 10178
Main Authors Zhang, Hao, Chen, Pinhong, Liu, Guosheng
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 15.09.2014
WILEY‐VCH Verlag
Wiley
Subjects
Aromatic compounds
aryl iodides
Bonding
Cascades
Catalysis
Chemistry
Chemistry, Multidisciplinary
CH activation
fluorine
Formations
Hydrocarbons, Fluorinated - chemical synthesis
Hydrocarbons, Fluorinated - chemistry
Hydrocarbons, Iodinated - chemistry
Iodides
Molecular Structure
Organometallic Compounds - chemistry
palladium
Palladium - chemistry
Physical Sciences
Science & Technology
Styrenes
Styrenes - chemical synthesis
Styrenes - chemistry
Synthesis
trifluoroethylation
C(SP)-H BONDS
ACTIVATION
ACIDS
ALKYLATION
aryl iodides
trifluoroethylation
FLUORINATION
REDUCTIVE ELIMINATION
INDOLES
FUNCTIONALIZATION
CROSS-COUPLING REACTIONS
C-H activation
palladium
fluorine
TRIFLUOROMETHYLATION
CH activation
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Summary:A palladium‐catalyzed selective CH bond trifluoroethylation of aryl iodides has been explored. The reaction allows for the efficient synthesis of a variety of ortho‐trifluoroethyl‐substituted styrenes. Preliminary mechanistic studies indicate that the reaction might involve a key PdIV intermediate, which is generated through the rate‐determining oxidative addition of CF3CH2I to a palladacycle; the bulky nature of CF3CH2I influences the reactivity. Reductive elimination from the PdIV complex then leads to the formation of the aryl–CH2CF3 bond. The palladium‐catalyzed selective CH bond trifluoroethylation of aryl iodides allows for an efficient synthesis of a variety of ortho‐trifluoroethyl‐substituted styrenes. Preliminary mechanistic studies indicate that the reaction might proceed through rate‐determining oxidative addition of CF3CH2I to a palladacycle.
Bibliography:We are grateful for financial support from the National Natural Science Foundation of China (21225210, 21121062, and 21202185), the National Basic Research Program of China (973-2011CB808700), the Science Technology Commission of the Shanghai Municipality (11JC1415000), and the CAS/SAFEA International Partnership Program for Creative Research Teams. H.Z. and G.L. thank Dr. Hao-yang Wang (SIOC) for his assistance with the mass spectrometry studies.
National Basic Research Program of China - No. 973-2011CB808700
istex:304BF1DCCB49D6D8810365FCDBBEDF0A4BE150E6
National Natural Science Foundation of China - No. 21225210; No. 21121062; No. 21202185
Science Technology Commission of the Shanghai Municipality - No. 11JC1415000
ArticleID:ANIE201403793
ark:/67375/WNG-608N9GPB-J
We are grateful for financial support from the National Natural Science Foundation of China (21225210, 21121062, and 21202185), the National Basic Research Program of China (973‐2011CB808700), the Science Technology Commission of the Shanghai Municipality (11JC1415000), and the CAS/SAFEA International Partnership Program for Creative Research Teams. H.Z. and G.L. thank Dr. Hao‐yang Wang (SIOC) for his assistance with the mass spectrometry studies.
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201403793