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Synlett 2011(2): 169-172  
DOI: 10.1055/s-0030-1259292
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

First Example of Quinoxaline-Directed C-H Activation: A Novel Method for Acetoxylation of Arenes

B. V. Subba Reddy*, K. Ramesh, J. S. Yadav
Division of Organic Chemistry, Indian Institute of Chemical Technology, Hyderabad 500 007, India
e-Mail: basireddy@iict.res.in;
Further Information

Publication History

Received 2 August 2010
Publication Date:
23 December 2010 (online)

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Abstract

2-Aryl- and 2,3-diarylquinoxalines undergo smooth acetoxylation in the presence of 5 mol% Pd(OAc)2 and a stoichiometric amount of PhI(OAc)2 via C-H activation to produce the corresponding acetoxy-susbstituted quinoxaline derivatives in excellent yields with high regioselectivity.

Key words

hypervalent iodine reagent - aryl quinoxalines - acetoxylation - C-H activation

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11

Typical Experimental Procedure
A mixture of 2,3-diphenylquinoxaline (100 mg, 0.35 mmol), PhI(OAc)2 (250 mg, 0.78 mmol), and Pd(OAc)2 (4 mg, 0.05 mmol) in DCE (5 mL) was stirred at r.t. for 10 min, then the resulting mixture was heated to 90 ˚C for 12 h. After completion of reaction as indicated by TLC, the reaction mixture was filtered, diluted with H2O and extracted with CH2Cl2 (2 × 15 mL). The combined organic layers were dried over anhyd Na2SO4, concentrated in vacuo, and purified by column chromatography on silica gel (Merck, 60-120 mesh, EtOAc-hexane, 0.5:9.5) to afford pure bisacetoxy derivative.
Compound 3c: yellow solid, mp 143-144 ˚C. IR (KBr):
νmax = 3027, 2923, 2854, 1765, 1620, 1458, 1370, 1190, 1116, 1031, 909, 758 cm-¹. ¹H NMR (300 MHz, CDCl3):
δ = 2.10 (s, 3 H), 2.48 (s, 3 H), 7.01-7.07 (m, 2 H), 7.24-7.30 (m, 2 H), 7.79 (s, 1 H). ¹³C NMR (75 MHz, CDCl3): δ = 20.3, 20.8, 123.0, 125.5, 128.8, 129.8, 131.3, 131.4, 139.8, 140.0, 148.2, 149.7, 168.9. MS (EI): m/z = 449 [M + Na]. HRMS: m/z calcd for C26H22N2O4Na: 449.1477; found: 449.1475.
Compound 3e: yellow solid, mp 161-162 ˚C. IR (KBr):
νmax = 3029, 2922, 2852, 1769, 1715,1442, 1374, 1310, 1278, 1254, 1181, 1112, 1054, 1027, 907, 807 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 2.09 (s, 3 H), 2.10 (s, 3 H), 4.03 (s, 3 H), 7.17 (m, 4 H), 7.41 (m, 4 H), 8.18 (s, 1 H), 8.39 (dd, 1 H, J = 1.8, 8.6 Hz), 8.85 (d, 1 H, J = 1.7 Hz). ¹³C NMR (75 MHz, CDCl3): δ = 20.8, 20.9, 52.6, 123.2, 125.6, 129.4, 129.8, 130.3, 130.6, 130.7, 131.4, 131.6, 131.7, 140.1, 142.7, 148.3, 151.9, 152.7, 166.1, 168.7, 168.8. MS (EI): m/z = 479 [M + Na]. HRMS: m/z calcd for C26H20N2O6Na: 479.1219; found: 479.1202.
Compound 3j: pale yellow solid, mp 103-104 ˚C. IR (neat): νmax = 3020, 2923, 2852, 1764, 1646, 1544, 1488, 1448, 1369, 1312, 1187, 1108, 1034, 1010, 958, 912, 867, 764 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 2.23 (s, 3 H), 7.21 (s, 1 H), 7.39-7.57 (m, 2 H), 7.74-7.80 (m, 2 H), 7.91 (dd, 2 H, J = 1.3, 6.2 Hz), 8.21 (m, 2 H), 9.10 (s, 1 H). ¹³C NMR (75 MHz, CDCl3): δ = 20.9, 123.5, 128.1, 129.1, 129.4 129.5, 129.9, 130.2, 130.3, 130.9, 131.1, 141.1, 148.5, 150.8, 169.3. MS (EI): m/z = 287 [M + Na]. HRMS: m/z calcd for C16H12N2O2Na: 287.0796; found: 287.0784.