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Synlett 2015; 26(12): 1677-1682
DOI: 10.1055/s-0034-1380210
DOI: 10.1055/s-0034-1380210
letter
Iodine-Mediated Domino Protocol for the Synthesis of Benzamides from Ethylarenes via sp3 C–H Functionalization
Further Information
Publication History
Received: 18 March 2015
Accepted: 04 April 2015
Publication Date:
21 May 2015 (online)
Dedicated to our mentor Prof. P. M. Bhate on the occasion of his 61st 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)Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1380210.
- Supporting Information
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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.