Synlett 2017; 28(19): 2581-2586
DOI: 10.1055/s-0036-1589126
cluster
© Georg Thieme Verlag Stuttgart · New York

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

Yong-Yuan Gui
a  Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, #29 Wangjiang Road, Chengdu 610064, P. R. of China   Email: dgyu@scu.edu.cn
,
Xiao-Wang Chen
a  Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, #29 Wangjiang Road, Chengdu 610064, P. R. of China   Email: dgyu@scu.edu.cn
,
a  Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, #29 Wangjiang Road, Chengdu 610064, P. R. of China   Email: dgyu@scu.edu.cn
b  College of Chemistry and Chemical Engineering, Neijiang Normal University, Neijiang 641112, P. R. of China   Email: chemzhwj@126.com
,
a  Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, #29 Wangjiang Road, Chengdu 610064, P. R. of China   Email: dgyu@scu.edu.cn
› Author Affiliations
We are grateful for financial support from the National Natural Science Foundation of China (21772129), the “973” Project from of the MOST of China (2015CB856600), the “1000-Youth Talents Plan”, and the Fundamental Research Funds for the Central Universities.
Further Information

Publication History

Received: 30 July 2017

Accepted after revision: 04 October 2017

Publication Date:
03 November 2017 (online)


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.

Supporting Information

 
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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); Rf = 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%); Rf = 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.