Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 84, Issue 14, Pages 9051-9057Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.9b00968
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Funding
- National Institutes of Health [GM131713]
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Aryl carbamates are orthometalated by sodium diisopropylamide (NaDA) in tetrahydrofuran. The resulting arylsodiums undergo Snieckus Fries rearrangement to give orthoacylated phenols in good yield. The intermediate arylsodiums and resulting orthoacylated phenolates are suggested to be monomeric. The rate-limiting step in the two-step sequence depends on the steric demands of the carbamoyl moiety and the substituents in the meta position of the arene. Rate studies reveal a dominant disolvated-monomer-based orthometalation followed by a di- or trisolvated arylsodium monomer-based rearrangement. Kinetic evidence of a NaDA-catalyzed Snieckus Fries rearrangement suggests the intermediacy of mixed trimers. Competitive halide eliminations to form benzyne are also discussed.
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