Catalyst-Tuned Electrophilic Chlorination of Diverse Aromatic Compounds with Sulfuryl Chloride and Regioselective Chlorination of Phenols with Organocatalysts
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Tarih
2022
Yazarlar
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Amer Chemical Soc
Erişim Hakkı
info:eu-repo/semantics/closedAccess
Özet
In this work, we demonstrate that diverse aromatic compounds can be selectively chlorinated through the fine-tuning of the reactivity of sulfuryl chloride (SO2Cl2) by organocatalysts. Acetonitrile has been identified to activate SO2Cl2 most strongly, thus enabling even chlorination of p-xylene with high yields. 1,4-Dioxane effects chlorination of oxidation-labile aromatic compounds such as p-cresol and 2-naphthol with high yields, 95% and 85%, respectively. An array of potential catalysts has been screened for ortho- and para-selective chlorination of phenols. Thus, we found that acetonitrile, (S)-BINAPO (5 mol %), and diisopropyl ether (4.00 equiv) can catalyze the chlorination of phenols in a para-selective manner (with <= 4:96 o:p ratio), whereas Nagasawa's bis-thiourea (1 mol %), phenyl boronic acid (5 mol %), and (S)-diphenylprolinol (1 mol %) exhibit high ortho selectivity [with <= 99:1 o:p ratio by (S)-diphenylprolinol].
Açıklama
Anahtar Kelimeler
Lewis-Base Catalysis, Selective Chlorination, Carbonyl-Compounds, Alpha-Arylation, Bronsted Acid, Chemistry, Halogenation, Reactivity, Biology, Ketones
Kaynak
Journal of Organic Chemistry
WoS Q Değeri
Q1
Scopus Q Değeri
Q2
Cilt
87
Sayı
19
