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Synlett 2013; 24(11): 1423-1427
DOI: 10.1055/s-0033-1338453
DOI: 10.1055/s-0033-1338453
letter
Copper-Catalyzed Formamidation of Arylboronic Acids: Direct Access to Formanilides
Further Information
Publication History
Received: 19 March 2013
Accepted after revision: 08 April 2013
Publication Date:
08 May 2013 (online)
Abstract
A new approach for direct synthesis of formanilides starting from structurally varied arylboronic acids is reported. The protocol involves a copper-catalyzed Chan–Lam coupling reaction between arylboronic acids and formamide in the presence of a base at room temperature. The strategy offers a valid and practical alternative to existing transformations of amino, nitro, and azido arenes to formanilides, especially in terms of executing arylboronic acids as easily accessible, stable, and diversified substrates, under mild reaction conditions, and in a simple operation with high efficiency.
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- 25 General Procedure for the Synthesis of Formanilides 2 To an open flask containing a solution of arylboronic acid 1 (1.0 mmol) in formamide (2 mL) were added Cu(OAc)2·H2O (19.9 mg, 10 mol%) and K2CO3 (138.2 mg, 1 mmol), and the mixture was stirred vigorously at r.t. under air (without bubbling air) for 8–16 h (Table 2). After completion of the reaction (indicated by TLC), the reaction mixture was treated with EtOAc (5 mL) and H2O (5 mL). The organic layer was separated, and the aqueous layer was extracted with EtOAc (3 × 5 mL). The combined organic phase was washed with H2O (2 × 5 mL), dried over anhyd Na2SO4, and concentrated to yield a residue, which was purified by flash chromatography (prepacked silica cartridges) to afford the clean product 2 as a mixture of rotamers.27 All the products are known compounds and were characterized by comparison of their melting points and spectral data with those reported in the literature.14–17 As a typical example, the data for 2a are given. N-Phenylformamide (2a, Table 2) Isolated as a pale brownish solid (109 mg, 90%); mp 48–49 °C [lit.17a 47–48 °C]. 1H NMR (400 MHz, CDCl3): δ = 9.12 (br s, 1 H, NH), 8.70 (d, J = 11.4 Hz, 1 H, CHO), 8.39 (s, 1 H, CHO), 8.10 (br s, 1 H, NH), 7.54 (d, J = 7.8 Hz, 2 H, ArH), 7.39–7.31 (m, 4 H, ArH), 7.20–7.14 (m, 2 H, ArH), 7.09 (d, J = 7.7 Hz, 2 H, ArH). 13C NMR (100 MHz, CDCl3): δ = 163.1, 159.5, 137.0, 136.7, 129.8, 128.9, 125.0, 124.6, 119.9, 118.6. IR (KBr): 3252, 3048, 1686, 1602, 1550, 1430, 1352, 758, 710, 696 cm–1. MS (EI): m/z = 122 [M+ + 1]. Anal. Calcd for C7H7NO: C, 69.41; H, 5.82; N, 11.56. Found: C, 69.16; H, 5.96; N, 11.48.
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