Transition-Metal-Free C–N Bond Activation: Synthesis of α,α-Bis(arylthio) Aldehydes

Abstract

A novel and convenient tandem reaction of I₂-catalzyed C–N bond activation of tertiary amines and subsequent aryl thiolation has been explored. A variety of disulfides and series of tertiary amines were efficiently converted into the corresponding α,α-bis(arylthio) aldehydes in moderate to good yields. The reaction proceeded well under transition-metal-free conditions via a C–N activation process.

Key words

disulfides - transition-metal-free - α,α-bis(arylthio) aldehydes - tertiary amine - radicals

• References

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• 17 Typical Procedure Under air atmosphere, a reaction tube was charged with disulfane (0.2 mmol), tertiary amine (0.4 mmol), I₂ (0.4 mmol), Na₂CO₃ (0.4 mmol), and DMSO (2 mL). The vessel was sealed and heated at 100 °C (oil bath temperature) for 24 h and then cooled to r.t. The reaction mixture was washed with sat. Na₂S₂O₃ (2 × 15 mL) and then brine (1 × 15 mL). After the aqueous layer was extracted with EtOAc, the combined organic layers were dried over anhydrous Na₂SO₄ and evaporated under vacuum. The residue was purified by flash column chromatography (hexane–EtOAc) to afford the desired products 3. 2,2-Bis(phenylthio)acetaldehyde (3) Yellow oil (41.6 mg, 80% yield). ¹H NMR (500 MHz, CDCl₃): δ = 9.28 (d, J = 4.5 Hz, 1 H), 7.48 (dd, J = 6.6, 2.9 Hz, 4 H), 7.34–7.32 (m, 6 H), 4.72 (d, J = 4.5 Hz, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 189.4, 133.6, 130.9, 129.3, 128.9, 62.0. IR (ATR): ν = 3015, 2976, 1717, 1539, 1469, 1362, 1230, 1025, 737, 689 cm^–1. ESI-HRMS: m/z calcd for C₁₄H₁₂NaOS₂ ⁺ [M + Na]⁺: 283.0222; found: 283.0216.