Iodine-Mediated Domino Protocol for the Synthesis of Benz­amides from Ethylarenes via sp³ C–H Functionalization

Dedicated to our mentor Prof. P. M. Bhate on the occasion of his 61^st birthday

Abstract

An efficient, metal-free domino protocol for the synthesis of benzamides has been developed from ethylarenes using aqueous ammonia. The reaction proceeds through the formation of triiodomethyl ketone intermediate in the presence of iodine as the promoter and TBHP as an oxidant followed by nucleophilic substitution with aqueous ammonia, forming an amide. This operationally simple, functional-group-tolerant tandem approach provides an easy access to the broad range of biologically important benzamides.

Key words

sp³ C–H functionalization - benzamides - iodine - ethyl­arenes - tert-butyl hydroperoxide (TBHP)

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• 23 General Procedure for the Oxidative Amidation of Ethylarenes A sealed tube equipped with a magnetic stirring bar was charged with ethylarene (1, 1.0 mmol), aq NH₃ (2, 25% aq solution, 10.0 mmol), I₂ (1.1 mmol), and TBHP (6.0 mmol, 70% aq solution) at r.t. The resulting mixture was heated to 100 °C for 3.0 h. After completion of the reaction (monitored by TLC), sat. Na₂S₂O₃ solution (10 mL) was added to the reaction mixture, and it was extracted with EtOAc (2 × 20 mL). The organic layer was washed with brine solution (20 mL), dried over anhydrous Na₂SO₄ and concentrated under reduced pressure. The residue was purified by column chromatography on 100–200 mesh silica gel using EtOAc–n-hexane (1:2) as the eluent to obtain the corresponding benzamide 3.