The regioexhaustive functionalization of difluorophenols and trifluorophenols through organometallic intermediates

2,4-Difluorophenol, 2,5-difluorophenol, 2,3-difluorophenol, 3,5-difluorophenol, 3,4-difluorophenol, 2,4,5-trifluorophenol and 2,3,4-trifluorophenol were converted into all 18 possible di- or trifluorinated hydroxybenzoic acids, all of them new compds. The phenolic hydrogen atom was replaced by a methoxymethyl or, less frequently, by a triisopropylsilyl group, which exerted an ortho activating or ortho shielding effect, resp. Sites flanked by two electroneg. substituents (fluorine, alkoxy) were deprotonated with particular ease. They had to be silenced by the reversible attachment of a metalation-blocking trimethylsilyl group or of a metalation-deflecting chlorine atom if the metal was to be introduced elsewhere. In all cases but one, the stage was thus set for an intramol. competition between metalation at an oxygen-adjacent or a fluorine-adjacent site. It proved indeed possible to secure the desired regioflexibility in either way by relying on an appropriate substrate-reagent matching. This demonstrates once more the potential of the organometallic approach to diversity-oriented synthesis. [on SciFinder (R)]


Published in:
Synthesis, 10, 1609-1618
Year:
2004
Keywords:
Note:
CAN 141:243137
25-17
Benzene, Its Derivatives, and Condensed Benzenoid Compounds
Institut des Sciences et Ingenierie Chimiques (ISIC, BCh),Ecole Polytechnique Federale,Lausanne,Switz.
Journal
0039-7881
written in English.
107-30-2 (Chloromethyl methyl ether); 367-27-1 (2,4-Difluorophenol); 2268-16-8 (2,4,5-Trifluorophenol); 2713-31-7 (2,5-Difluorophenol); 2713-33-9 (3,4-Difluorophenol); 2713-34-0 (3,5-Difluorophenol); 2822-41-5 (2,3,4-Trifluorophenol); 6418-38-8 (2,3-Difluorophenol); 13154-24-0 (Chlorotriisopropylsilane) Role: RCT (Reactant), RACT (Reactant or reagent) (regioexhaustive functionalization of difluorophenols and trifluorophenols through organometallic intermediates); 210350-62-2P; 749230-16-8P; 749230-18-0P; 749230-20-4P; 749230-22-6P; 749230-24-8P; 749230-26-0P; 749230-28-2P; 749230-30-6P; 749230-34-0P; 749230-36-2P; 749230-38-4P; 749230-39-5P; 749230-41-9P; 749230-42-0P; 749230-43-1P; 749230-44-2P; 749230-46-4P; 749230-48-6P; 749230-49-7P; 749230-50-0P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (regioexhaustive functionalization of difluorophenols and trifluorophenols through organometallic intermediates); 20483-55-0P; 38233-44-2P; 84376-20-5P; 91659-22-2P; 146781-23-9P (2,5-Difluoro-4-hydroxybenzoic Acid); 175968-39-5P (2,3-Difluoro-4-hydroxybenzoic Acid); 189283-51-0P (3,4-Difluoro-2-hydroxybenzoic Acid); 189283-54-3P; 205533-30-8P (3,4,5-Trifluoro-2-hydroxybenzoic Acid); 205533-31-9P (4,5-Difluoro-2-hydroxybenzoic Acid); 214917-68-7P (2,6-Difluoro-4-hydroxybenzoic Acid); 749230-32-8P; 749230-35-1P; 749230-37-3P; 749230-40-8P; 749230-45-3P; 749230-47-5P; 749230-51-1P; 749230-52-2P Role: SPN (Synthetic preparation), PREP (Preparation) (regioexhaustive functionalization of difluorophenols and trifluorophenols through organometallic intermediates)
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 Record created 2006-03-03, last modified 2018-01-27


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