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Synlett 2012; 23(18): 2714-2718
DOI: 10.1055/s-0032-1317350
DOI: 10.1055/s-0032-1317350
letter
Direct Oxidative C–H Arylation of Benzoxazoles with Arylsulfonyl Hydrazides Promoted by Palladium Complexes
Further Information
Publication History
Received: 21 August 2012
Accepted after revision: 11 September 2012
Publication Date:
09 October 2012 (online)
Abstract
This study describes a direct oxidative C-2 arylation of benzoxazoles using arylsulfonyl hydrazides as the aryl sources. A simple catalyst system [Pd(OAc)2 and Ph3P] allows the reactions to proceed smoothly under oxidative reaction conditions. Other heteroarenes such as caffeine and benzothiazole are also applicable substrates. Notably, this catalytic system tolerates halogen substituents which provides a useful complement to the current cross-coupling reactions which use aryl halides.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
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- 10 Representative Experimental Procedures: All reagents were weighted in air and the reactions were performed in an open vessel (60 mL vial equipped with an air condenser). Pd(OAc)2 (0.0034 g, 0.015 mmol), Ph3P (Pd/L = 1:2), arylsulfonyl hydrazides (0.45 mmol), heteroarenes (0.3 mmol) and Cu(OAc)2 (0.6 mmol) were loaded into a 60 mL vial equipped with a Teflon-coated magnetic stir bar. Dioxane (3 mL) was added at r.t. The vial was fitted with an air condenser and then placed into a preheated oil bath with the reaction temperature indicated in the table and the reaction mixture was vigorously stirred for 18 h. After the completion of reaction, the reaction vial was allowed to cool to r.t. EtOAc (ca. 20 mL) and H2O (ca. 10 mL) were added. The organic layer was subjected to GC analysis. After analyzing the GC spectra, the crude product in the organic layer was extracted and the vial was washed with EtOAc. The filtrate was concentrated under reduced pressure. The crude product was purified by flash column chromatography on silica gel (230–400 mesh) to afford the desired product. 2-Phenylbenzoxazole (Table 2, entry1, compound 3aa): eluent: EtOAc–hexane (1:20; Rf 0.62) was used for flash column chromatography to provide compound 3aa (44.5 mg, 76 % yield) as a white solid. 1H NMR (400 MHz, CDCl3): δ = 7.36–7.40 (m, 2 H), 7.52–7.57 (m, 3 H), 7.58–7.63 (m, 1 H), 7.79–7.83 (m, 1 H), 8.28–8.31 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ = 110.5, 120.0, 124.5, 125.1, 127.1, 127.6, 128.8, 131.5, 142.0, 150.7, 163.0. MS (EI): m/z (relative intensity) = 195.0 (100) [M+], 167.0 (18), 139.0 (3), 92.0 (5), 63.0 (14).
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