Structure‐reactivity relationship of benzyl benzenesulfonates. Part 3. Prediction of reaction mechanism by the use of correlation interaction coefficients

Exploiting Differences in Solution vs Solid-Supported Reactivity for the Synthesis of Sulfonic Acid Derivatives

“…Treatment of either the butanesulfonate-functionalized or p -toluenesulfonate-functionalized resin with a solution of triethylamine (0.72 M), DBU (0.67 M), pyridine (1.24 M), or tetramethylguanidine (TMG) (0.8 M) in acetonitrile, methanol, methylene chloride, or DMF at room temperature caused little or no loss of compound from the resin, as judged by examining HPLC traces of the eluent and verified by subsequent cleavage and isolation of the product (Table ). This was an unexpected result and is contrary to the known high reactivity of benzyl tosylates in solution-phase nucleophilic displacements . For example, in our hands treatment of benzyl tosylate with a 0.7 M solution of triethylamine in acetonitrile resulted in quantitative loss of starting material after 15 min at room temperature.…”