Buttressing Effects on Haloarene Deprotonation: A Merely Kinetic or Also Thermodynamic Phenomenon?
2004
Abstract
(2,6-Dichlorophenyl)- and (2,6-dibromophenyl)trialkylsilanes undergo hydrogen/metal interconversion preferentially at the 4- rather than 3-position. However, the organometallic species generated by such a \"meta metalation\" are thermodynamically less stable (i.e., more basic) than those that would result from an ordinary \"ortho metalation\". This was demonstrated by equilibration expts. based on permutational halogen/metal interconversion. A new buttressing effect can explain the unprecedented regioselectivity. It is supported by X-ray structures that reveal marked deformations of the benzene ring in halophenylsilanes. [on SciFinder (R)]
Details
Title
Buttressing Effects on Haloarene Deprotonation: A Merely Kinetic or Also Thermodynamic Phenomenon?
Author(s)
Gorecka, Joanna ; Heiss, Christophe ; Scopelliti, Rosario ; Schlosser, Manfred
Published in
Organic Letters
Volume
6
Issue
24
Pages
4591-4593
Date
2004
ISSN
1523-7060
Keywords
Deprotonation; Steric effects (buttressing effects on haloarene deprotonation kinetics or thermodn. phenomenon); Aromatic hydrocarbons Role: CPS (Chemical process); FMU (Formation; unclassified); PEP (Physical; engineering or chemical process); PRP (Pro; buttressing effect haloarene deprotonation kinetic thermodn phenomenon
Note
CAN 142:22985
22-12
Physical Organic Chemistry
Institute of Chemical Sciences and Engineering (ISIC),Ecole Polytechnique Federale,Lausanne,Switz.
Journal
written in English.
17989-28-5; 121412-28-0 ((2,4-Dichlorophenyl)lithium); 802984-56-1; 802984-57-2 Role: CPS (Chemical process), FMU (Formation, unclassified), PEP (Physical, engineering or chemical process), RCT (Reactant), FORM (Formation, nonpreparative), PROC (Process), RACT (Reactant or reagent) (buttressing effects on haloarene deprotonation kinetics or thermodn. phenomenon); 19752-55-7 (3,5-Dichloro-1-bromobenzene); 650598-50-8 (4-Triethylsilyl-3,5-dichloro-1-bromobenzene) Role: FMU (Formation, unclassified), FORM (Formation, nonpreparative) (buttressing effects on haloarene deprotonation kinetics or thermodn. phenomenon); 802984-55-0P Role: FMU (Formation, unclassified), PRP (Properties), SPN (Synthetic preparation), FORM (Formation, nonpreparative), PREP (Preparation) (buttressing effects on haloarene deprotonation kinetics or thermodn. phenomenon); 1193-72-2 (1-Bromo-2,4-dichlorobenzene) Role: FMU (Formation, unclassified), RCT (Reactant), FORM (Formation, nonpreparative), RACT (Reactant or reagent) (buttressing effects on haloarene deprotonation kinetics or thermodn. phenomenon); 802984-53-8P; 802984-54-9P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (buttressing effects on haloarene deprotonation kinetics or thermodn. phenomenon); 108-18-9 (Diisopropylamine); 3032-81-3; 29898-32-6; 650598-44-0 Role: RCT (Reactant), RACT (Reactant or reagent) (buttressing effects on haloarene deprotonation kinetics or thermodn. phenomenon); 650598-42-8 (3,5-Dibromo-4-triethylsilylbenzoic acid) Role: PRP (Properties) (crystal structure; of 3,5-dibromo-4-triethylsilylbenzoic acid); 650598-41-7 (3,5-Dichloro-4-triethylsilylbenzoic acid) Role: PRP (Properties) (crystal structure; of 3,5-dichloro-4-triethylsilylbenzoic acid)
22-12
Physical Organic Chemistry
Institute of Chemical Sciences and Engineering (ISIC),Ecole Polytechnique Federale,Lausanne,Switz.
Journal
written in English.
17989-28-5; 121412-28-0 ((2,4-Dichlorophenyl)lithium); 802984-56-1; 802984-57-2 Role: CPS (Chemical process), FMU (Formation, unclassified), PEP (Physical, engineering or chemical process), RCT (Reactant), FORM (Formation, nonpreparative), PROC (Process), RACT (Reactant or reagent) (buttressing effects on haloarene deprotonation kinetics or thermodn. phenomenon); 19752-55-7 (3,5-Dichloro-1-bromobenzene); 650598-50-8 (4-Triethylsilyl-3,5-dichloro-1-bromobenzene) Role: FMU (Formation, unclassified), FORM (Formation, nonpreparative) (buttressing effects on haloarene deprotonation kinetics or thermodn. phenomenon); 802984-55-0P Role: FMU (Formation, unclassified), PRP (Properties), SPN (Synthetic preparation), FORM (Formation, nonpreparative), PREP (Preparation) (buttressing effects on haloarene deprotonation kinetics or thermodn. phenomenon); 1193-72-2 (1-Bromo-2,4-dichlorobenzene) Role: FMU (Formation, unclassified), RCT (Reactant), FORM (Formation, nonpreparative), RACT (Reactant or reagent) (buttressing effects on haloarene deprotonation kinetics or thermodn. phenomenon); 802984-53-8P; 802984-54-9P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (buttressing effects on haloarene deprotonation kinetics or thermodn. phenomenon); 108-18-9 (Diisopropylamine); 3032-81-3; 29898-32-6; 650598-44-0 Role: RCT (Reactant), RACT (Reactant or reagent) (buttressing effects on haloarene deprotonation kinetics or thermodn. phenomenon); 650598-42-8 (3,5-Dibromo-4-triethylsilylbenzoic acid) Role: PRP (Properties) (crystal structure; of 3,5-dibromo-4-triethylsilylbenzoic acid); 650598-41-7 (3,5-Dichloro-4-triethylsilylbenzoic acid) Role: PRP (Properties) (crystal structure; of 3,5-dichloro-4-triethylsilylbenzoic acid)
Other identifier(s)
DAR: 5884
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Laboratories
LSCO
Record Appears in
Scientific production and competences > SB - School of Basic Sciences > SB Archives > LSCO - Laboratory of Organic Synthesis and Catalysis
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Work produced at EPFL
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Published
Peer-reviewed publications
Work produced at EPFL
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Published
Record creation date
2006-03-03