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Synlett 2023; 34(03): 253-258
DOI: 10.1055/a-1961-8083
DOI: 10.1055/a-1961-8083
letter
Exploration of Copper(II) Acetate Catalyzed Regioselective Ethoxylation of o-Haloanilides with Picolinamide as a Directing Group
This work was financially supported by the Yunnan Provincial Science and Technology Department-Applied Basic Research Joint Special Funds of Yunnan University of Chinese Medicine (202001AZ070001-007, 202101AZ070001-055).
Abstract
An efficient Cu-catalyzed Ullmann-type C–O coupling of o-haloanilides was developed. This method permits regioselective 2-ethoxylation of N-(2-bromoaryl)- or N-(2-iodoaryl)picolinamides in ethanol with Cu(OAc)2 as a convenient catalyst and with picolinamide as a directing group and intramolecular ligand. The reaction is characterized by good regioselectivity, high yields, and the absence of the need for an additional ligand.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1961-8083.
- Supporting Information
Publication History
Received: 05 September 2022
Accepted after revision: 17 October 2022
Accepted Manuscript online:
17 October 2022
Article published online:
15 December 2022
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- 18 Ethoxylation of o-Haloanilides; General Procedure A stirred solution of the appropriate o-haloanilide 1 (1 mmol), Cu(OAc)2 (20 mg, 0.1 mmol), and K2CO3 (276 mg, 2 mmol) in EtOH (10 mL) was stirred at 100 °C for 8–12 h. When the reaction was complete (TLC), the mixture was concentrated in vacuo, and the residue was purified by column chromatography [silica gel, PE–EtOAc (5:1)]. N-(2-Ethoxyphenyl)picolinamide (2a) Prepared according to the general procedure from 1a or 1a′ as a pale-yellow thick liquid; yield: 85 or 90%, respectively. 1H NMR (400 MHz, CDCl3): δ = 10.67 (s, 1 H), 8.63 (d, J = 5.7 Hz, 2 H), 8.29 (d, J = 7.8 Hz, 1 H), 7.85–7.88 (m, 1 H), 7.41–7.44 (m, 1 H), 6.99–7.08 (m, 1 H), 6.92 (d, J = 7.8 Hz, 1 H), 4.18 (q, J = 7.0 Hz, 2 H), 1.53 (t, J = 7.0 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 162.06, 150.49, 148.28, 148.20, 137.49, 127.94, 126.22, 123.97, 122.30, 121.09, 119.74, 111.50, 64.51, 14.91.