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Synlett 2018; 29(01): 79-84
DOI: 10.1055/s-0036-1591210
DOI: 10.1055/s-0036-1591210
letter
Copper(I) Iodide-Catalyzed (Het)arylation of Diethyl Malonate with (Het)aryl Bromides by Using 1,3-Benzoxazole as a Ligand
Authors
The research has been supported by National Natural Science Foundation of China (Grant No.U1463201, 21522604 and 21402240) and Jiangsu Province Natural Science Fund (Grant No.BK20150031)
Further Information
Publication History
Received: 20 June 2017
Accepted after revision: 26 July 2017
Publication Date:
26 October 2017 (online)
Abstract
An efficient Ullmann-type coupling of aryl bromides with diethyl malonate in the presence of copper(I) iodide and 1,3-benzoxazole is presented. This method has a broad substrate scope (heterocyclic and phenyl bromides) and good functional-group tolerance (OMe, Me, Ac, CN, NO2, F, and Cl). Moreover, less time is needed to reach full conversion (3–9 hours).
Key words
Ullmann coupling - benzoxazole - copper catalysis - aryl bromides - hetarylation - arylationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1591210.
- Supporting Information (PDF)
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- 15 Diethyl (Het)arylmalonates 3a–v; General Procedure DMSO (2 mL), the appropriate (het)aryl bromide 1 (1.0 mmol), diethyl malonate (2; 1.5 mmol), CuI (0.1 mmol), 1,3-benzoxazole (0.2 mmol), and K3PO4 (3 mmol) were successively added to a sealed tube under argon. The mixture was stirred at 50 °C for 3–9 h until the reaction was complete (TLC) and then poured into sat. aq NH4Cl (20 mL). The mixture was extracted with EtOAc (3 × 20 mL), and the organic phases were combined and washed with sat. aq NH4Cl (2 × 20 mL) and H2O (2 × 20 mL). The separated organic layer was then dried (Na2SO4), filtered, and concentrated under reduced pressure. The residue was purified by chromatography (silica gel, hexane/EtOAc). Diethyl Pyridin-3-ylmalonate (3a) Purified by column chromatography [silica gel, hexane/EtOAc (6:1)] to give a yellowish oil; yield: 204 mg (86%). 1H NMR (400 MHz, CDCl3): δ = 8.55–8.51 (m, 2 H), 7.80 (dt, J = 8.0, 2.0 Hz, 1 H), 7.27 (dd, J = 7.9, 4.8 Hz, 1 H), 4.59 (s, 1 H), 4.24–4.11 (m, 4 H), 1.21 (t, J = 7.1 Hz, 6 H). 13C NMR (101 MHz, CDCl3): δ = 167.43, 150.28, 149.53, 136.93, 128.97, 123.52, 62.19, 55.43, 13.97. HRMS (TOF): m/z [M + H]+ calcd for C12H15NO4: 238.1074; found: 238.1084.