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Synlett 2018; 29(18): 2432-2436
DOI: 10.1055/s-0037-1610293
DOI: 10.1055/s-0037-1610293
letter
(Diacetoxyiodo)benzene-Mediated Transition-Metal-Free Amination of C(sp3)–H Bonds Adjacent to Heteroatoms with Azoles: Synthesis of N-Alkylated Azoles
We thank the National Natural Science Foundation of China (Grant No. 21606202) for financial support. We are also grateful to the College of Pharmaceutical Sciences, Zhejiang University of Technology and the Advanced Research Fund for the Doctoral Program of Zhejiang Province for their financial help.Further Information
Publication History
Received: 29 August 2018
Accepted after revision: 04 September 2018
Publication Date:
01 October 2018 (online)
Abstract
A novel PhI(OAc)2-mediated cross-dehydrogenative coupling reaction of α-C(sp3)–H bonds adjacent to a hetero atom with various azoles has been developed, which provides an alternative method for constructing C–N bonds with high atom efficiency. This new protocol requires no metal catalyst and it provides ready access to a wide range of N-alkylated azole derivatives in moderate to excellent yields by using commercially available PhI(OAc)2 as the sole oxidant. Furthermore, the method is effective on a gram scale, which highlights the practicality of this transformation. The result of radical-captured experiments indicated that the transformation might involve a free-radical pathway.
Key words
diacetoxyiodo benzene - C–H functionalization - C–N bond - azoles - metal-free - aminationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610293.
- Supporting Information
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- 11 1-(3,4-Dihydro-1H-isochromen-1-yl)-1H-benzimidazole (3aa; Ref. 6); Typical Procedure PhI(OAc)2 (0.5 mmol) was added to a mixture of 1H-benzimidazole (1a; 0.5 mmol), isochroman (2a; 2.0 mmol), and DCE (2.0 mL) in a Schlenk tube at r.t. The mixture was stirred at 80 °C for 6 h then cooled. H2O (10 mL) was added, and the mixture was extracted with CH2Cl2 (3 × 10 mL). The combined organic layer was dried (Na2SO4) and concentrated under reduced pressure. The residues were purified by flash column chromatography (silica gel, hexane–EtOAc) to give a colorless oil; yield: 115 mg (92%). 1H NMR (600 MHz, CDCl3): δ = 7.86–7.83 (m, 1 H), 7.65 (s, 1 H), 7.48–7.46 (m, 1 H), 7.40 (t, J = 7.2 Hz, 1 H), 7.35–7.31 (m, 3 H), 7.27 (t, J = 7.2 Hz, 1 H), 7.09 (d, J = 7.8 Hz, 1 H), 6.94 (s, 1 H), 4.02–3.98 (m, 1 H), 3.87–3.83 (m, 1 H), 3.17–3.12 (m, 1 H), 2.91–2.87 (m, 1 H). 13C NMR (150 MHz, CDCl3): δ = 144.2, 142.7, 135.0, 133.8, 130.3, 129.4, 129.2, 127.1, 127.0, 123.4, 122.8, 120.4, 111.1, 80.2, 60.1, 27.7. MS (ESI): m/z = 251.1 [M + H]+.