Palladium-Catalyzed Highly Regioselective ortho-Halogenation of 2-Pyridyl Sulfoxides

^◊ These two authors contributed equally to this work

Abstract

A palladium-catalyzed regioselective ortho-halogenation of 2-pyridyl sulfoxides via a C–H activation pathway has been reported. Under the conditions established, this reaction proceeded smoothly and could tolerate a variety of functional groups under mild conditions.

Key words

palladium-catalyzed - regioselectivity - halogenation - C–H activation - sulfoxides

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• 20 General Procedure for the ortho-Iodination of 2-Pyridyl Sulfoxides with NIS A mixture of 2-pyridyl sulfoxides (40.6 mg, 0.2 mmol, 1.0 equiv), NIS (49.5 mg, 0.22 mmol, 1.1 equiv), TFA (11.4 mg, 0.1 mmol, 0.5 equiv), and Pd(OAc)₂ (4.5 mg, 0.02 mmol, 10 mol %) in PhCl (1 mL) was stirred under air at 80 °C for 20 h. The reaction mixture was cooled to r.t., then the volatiles were removed under reduced pressure. The contents were subjected to flash chromatography to give the corresponding product (60.0 mg, 85%) as pale yellow solid. The purified material was dried under an oil-pump vacuum. 2-[(2-Iodophenyl)sulfinyl]pyridine (2a) Pale yellow solid. ¹ H NMR (400 MHz, CDCl₃): δ = 8.58 (dd, J = 0.8, 4.0 Hz, 1 H), 7.96 (d, J = 8.0 Hz, 1 H), 7.87 (dd, J = 2.0, 8.0 Hz, 1 H), 7.85–7.83 (m, 1 H), 7.80 (dd, J = 1.6, 8.0 Hz, 1 H), 7.52 (dt, J = 1.2, 8.0 Hz, 1 H), 7.36–7.33 (m, 1 H), 7.17 (dt, J = 1.6, 8.0 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 164.81, 150.09, 147.09, 139.59, 137.95, 132.67, 129.21, 127.34, 125.14, 120.49, 94.66. ESI-HRMS: m/z [M + Na]⁺ calcd for C₁₁H₈INOSNa⁺: 351.9296; found: 351.9272.
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