Regioselective Cross-Dehydrogenative Coupling of Indole-2-carboxylic Acids and Pyridine-N-oxides Followed by Protodecarboxylation

Abstract

Regioselective coupling at the ortho position rather than at the ipso position of heteroaryl carboxylic acids with pyridine N-oxide has been reported.

Key words

arylation - C–H activation - decarboxylation - heterobiaryl N-oxide - regioselective

• References and Notes

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• 14 General Procedure for the Preparation of Substituted Pyridine-N-oxide (3) A mixture of substituted pyridine N-oxide 1 (1 equiv), heteroaryl carboxylic acid 2 (2 equiv), Pd(OAc)₂ (10 mol%), pyridine (3 equiv), and Ag₂O (2.5 equiv) in DMF–MeCN (1:2, 6 mL) was stirred at 110 °C for 12 h. The reaction mixture was filtered through a Celite pad and the pad washed with EtOAc. The organic layer was washed with H₂O and brine, dried over Na₂SO₄, filtered, and concentrated in vacuo. The crude product was purified on either a CombiFlash Rf or a Grace Instruments chromatography system on Teledyne Isco RediSep Rf columns (normal phase, 12 g) with 2–4% MeOH in CH₂Cl₂ as eluent to obtain 3. Representative Analytical Data of Compound 3a ¹H NMR (400 MHz, CDCl₃): δ = 7.27–7.30 (m, 2 H), 7.40 (t, J = 7.6 Hz, 1 H), 7.52 (t, J = 8.4 Hz, 2 H), 7.61 (t, J = 8.4 Hz, 1 H), 7.73 (dd, J = 8.0 1.4 Hz, 1 H), 8.17 (dd, J = 8.0, 1.4 Hz, 1 H), 8.30 (d, J = 8.4 Hz, 2 H), 8.44 (d, J = 6.4 Hz, 1 H), 8.52 (dd, J = 4.8, 1.4 Hz, 1 H), 8.85 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 110.7, 119.3, 120.9, 123.9, 125.4, 126.1, 128.4, 128.9, 129.1, 130.4, 134.4, 139.9, 140.7, 143.0, 145.4, 146.8. LC–MS [M + 1]: 352. Anal. Calcd for: C₁₈H₁₃N₃O₃S: C, 61.53; H, 3.73; N, 11.96. Found: C, 61.50; H, 3.77; N, 11.90.