Erturk, ErkanYesil, Tolga A.2025-03-232025-03-2320220022-32631520-6904https://doi.org/10.1021/acs.joc.2c00230https://hdl.handle.net/11486/5953In 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].eninfo:eu-repo/semantics/closedAccessLewis-Base CatalysisSelective ChlorinationCarbonyl-CompoundsAlpha-ArylationBronsted AcidChemistryHalogenationReactivityBiologyKetonesArticle8719125581257310.1021/acs.joc.2c0023036137270Q2WOS:000861630800001Q1