Copper-Catalyzed Benzylic sp3 C-H Amination Reaction of Amidines: Synthesis of Quinazoline Derivatives

doi:10.6023/A14080584

Abstract

Quinazoline motif is an important heterocyclic framework, which widely exists in many biologically active molecules and natural products. Although numerous synthetic efforts have been made for the preparation of quinazoline derivatives in recent years, it is still highly desirable to search for a more convenient and efficient approach. As part of our ongoing interest in transition-metal-catalyzed C—H functionalization, herein, we report a novel copper-catalyzed synthesis of quinazoline derivatives from amidines. During these transformations, the selectivity of benzylic sp³ C—H over aryl sp² C—H bond was efficiently realized. Various 2-arylquinazoline derivatives were obtained in moderate to good yields. A representative procedure for the copper-catalyzed construction of quinazolines from amidines is as following: N-(o-tolyl)benzimidamide (1a, 0.4 mmol, 89.7 mg), Cu(OTf)₂ (0.04 mmol, 13.8 mg) and Ag₂CO₃ (0.8 mmol, 219 mg) were added to a 25 mL sealed tube, followed by addition of DMF (2 mL). The mixture was stirred at 140 ℃ for 10 h. After cooling to room temperature, the mixture was poured into ice-water and extracted with CH₂Cl₂ (15 mL×3). The combined organic layers were dried (Na₂SO₄), filtered over Celite, evaporated in vacuo. The residue was purified by a shot flash silica gel column chromatography (petroleum ether/ethyl acetate, V:V=15:1) to afford the product 2a (71%, 62.4 mg).

Key words: copper, N-arylamidines, C—N bond formation, quinazoline derivatives

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Zhang Qian, Lü Yunhe, Li Yan, Xiong Tao, Zhang Qian. Copper-Catalyzed Benzylic sp³ C-H Amination Reaction of Amidines: Synthesis of Quinazoline Derivatives[J]. Acta Chim. Sinica, 2014, 72(11): 1139-1143.

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铜催化脒类化合物苄位sp³C—H键胺化反应:合成喹唑啉衍生物

Copper-Catalyzed Benzylic sp³ C-H Amination Reaction of Amidines: Synthesis of Quinazoline Derivatives

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