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Synlett 2014; 25(5): 665-670
DOI: 10.1055/s-0033-1340623
DOI: 10.1055/s-0033-1340623
letter
The Beckmann Rearrangement Executed by Visible-Light-Driven Generation of Vilsmeier–Haack Reagent
Further Information
Publication History
Received: 20 October 2013
Accepted: 17 December 2013
Publication Date:
15 January 2014 (online)
Abstract
A new and efficient approach for the Beckmann rearrangement is reported. The protocol involves eosin Y catalyzed, visible-light-mediated in situ formation of the Vilsmeier–Haack reagent from CBr4 and a catalytic amount of DMF for activation of ketoximes at room temperature. The method is operationally simple and avoids the need for any corrosive, water-sensitive reagents and elevated temperatures.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
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- 13 General Procedure for the Visible-Light-Driven Beckmann Rearrangement A mixture of ketoxime 1 (1.0 mmol), CBr4 (2.0 equiv), eosin Y (2 mol%), DMF (20 mol%), and MeCN (3 mL) was taken in an oven-dried round-bottom flask and irradiated with green LEDs while stirring under a nitrogen atmosphere. After completion of the reaction as indicated by TLC, it was quenched with sat. aq NaHCO3 (10 mL) and extracted with EtOAc (3 × 10 mL). The organic phase was dried over anhydrous MgSO4 and concentrated under reduced pressure to yield the crude product, which was purified by silica gel column chromatography (EtOAc–hexane) to give the corresponding amide 2 in high yield. All the products are known compounds and were characterized by comparison of their mp, TLC, 1H NMR, 13C NMR, and MS data with authentic samples obtained commercially or prepared by literature methods.7d,8d,9c,10a,14 The characterization data of the synthesized compounds 2 are summarized in the Supporting Information with relevant references.