Catalyst-Tuned Electrophilic Chlorination of Diverse Aromatic Compounds with Sulfuryl Chloride and Regioselective Chlorination of Phenols with Organocatalysts

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].