Arylation of Amide and Urea C(sp³)–H Bonds with Aryl Tosylates Generated In Situ from Phenols

Published as part of the Cluster C–O Activation

Abstract

The arylation of amide and urea C(sp³)–H bonds with aryl tosylates generated in situ from phenols has been realized at room temperature by combining visible-light-photoredox catalysis, hydrogen-atom-transfer catalysis, and nickel catalysis. This streamlined protocol permits rapid functionalization of phenols and direct transformation of α-amino C(sp³)–H bonds. The C(sp³)–H arylation products are obtained in high yields with good functional-group tolerance at low catalyst loadings.

Key words

phenols - arylation - amides - ureas - nickel catalysis - photocatalysis

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• 12 N-(4-Benzoylbenzyl)-N-methylformamide (3aa); Typical ProcedureA flame-dried, 10 mL Schlenk tube equipped with a magnetic stirrer bar was charged with Ir[dF(CF₃)ppy]₂(dtbbpy)(PF₆) (0.012 mmol). The tube was evacuated and filled with N₂ three times then transferred to a glovebox. NiBr₂·glyme (0.015 mmol), Me₄Phen (0.015 mmol), and Li₂CO₃ (0.6 mmol) were added to the tube, which was then transferring out of the glovebox and placed under an atmosphere of N₂. DMF (1a; 1.0 mL) was then added to the tube followed by 3-acetoxyquinuclidine (0.33 mmol). 4-Hydroxybenzophenone (2a) (0.3 mmol), TsCl (0.45 mmol), Cs₂CO₃ (0.6 mmol), and DMF (1a, 5.0 mL) were combined in a second 10 mL Schlenk tube and stirred at r.t. for 30 mins. This mixture was then filtered through an Acrodisc into the first Schlenk tube by using a syringe. The resulting mixture was degassed by three freeze–pump–thaw cycles, then placed at a distance of 3–5 cm from a 30 W blue LED and stirred at r.t. for 36 h. The solvent was then removed in vacuum and the crude product was purified by flash chromatography [silica gel (200–300 mesh), PE–EtOAc (5:1 to 1:1)] to give a pale-yellow oil; yield: 64.6 mg (85%, 0.255 mmol); R_f = 0.2 (PE–EtOAc, 1:1).¹H NMR (400 MHz, CDCl₃): δ = 8.27 (d, J = 46.8 Hz, 1 H), 7.87–7.76 (m, 4 H), 7.65–7.55 (m, 1 H), 7.49 (ddd, J = 8.5, 6.7, 3.9 Hz, 2 H), 7.39–7.30 (m, 2 H), 4.56 (d, J = 42.1 Hz, 2 H), 2.88 (d, J = 35.8 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 195.22, 195.03, 161.78, 161.68, 139.71, 139.44, 136.39, 136.25, 135.92, 131.62, 131.50, 129.65, 129.50, 128.97, 127.34, 127.29, 126.89, 126.18, 52.13, 46.54, 33.25, 28.65. HRMS (ESI): m/z [M + H]⁺ calcd. for C₁₆H₁₆NO₂: 254.1176; found: 254.1176. N-(4-Benzoylbenzyl)-N-methylacetamide (3ba)Pale-yellow oil; yield: 43.2 mg (0.162 mmol, 54%); R_f = 0.2 (PE–EtOAc, 1:1). ¹H NMR (400 MHz, CDCl₃): δ = 7.79 (dddd, J = 11.7, 8.1, 6.4, 1.9 Hz, 4 H), 7.64–7.55 (m, 1 H), 7.49 (td, J = 7.5, 5.8 Hz, 2 H), 7.39–7.27 (m, 2 H), 4.65 (d, J = 19.2 Hz, 2 H), 2.98 (s, 3 H), 2.18 (d, J = 10.9 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 195.27, 195.03, 169.99, 169.88, 141.15, 140.32, 136.47, 136.30, 135.97, 135.59, 131.56, 131.42, 129.73, 129.42, 128.95, 128.93, 127.32, 127.25, 126.63, 125.10, 53.02, 49.46, 34.84, 32.89, 20.76, 20.44. HRMS (ESI): m/z [M + H]⁺ calcd. for C₁₇H₁₈NO₂: 268.1332; found: 268.1332.