An Efficient Copper-Catalyzed
Microwave-Assisted S-Arylation towards the Synthesis of 8-Arylsulfanyl
Adenines

Weilin Sun; Pallav D. Patel; Ralph A. Stephani; Gabriela Chiosis

doi:10.1055/s-0031-1289888

LETTER

An Efficient Copper-Catalyzed Microwave-Assisted S-Arylation towards the Synthesis of 8-Arylsulfanyl Adenines

Weilin Sun^a, Pallav D. Patel^b, Ralph A. Stephani^b, Gabriela Chiosis*^a
^a Program in Molecular Pharmacology and Chemistry, Memorial Sloan-Kettering Cancer Center, New York, NY 10021, USA
Fax: +1(646)4220416; e-Mail: chiosisg@mskcc.org;
^b Department of Pharmaceutical Sciences, College of Pharmacy and Allied Health Professions, St. John’s University, Jamaica, NY 11439, USA

Abstract

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Abstract

We report a microwave-assisted synthetic protocol for the C-S cross-coupling reaction of aryl iodides and 8-mercaptoadenine using CuI and n-Bu₄NBr with NaOt-Bu in DMF. The method is rapid, simple, and cost efficient, and leads in high yields to biologically relevant aryl sulfides.

Key words

microwave - copper-catalyzed S-arylation - phase-transfer catalyst

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References and Notes

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General Procedure for the Microwave Coupling Reaction
In a conical-bottomed Biotage microwave vial, the mixture of 8-mercaptoadenine (16 mg, 0.1 mmol), 6-iodo-2,3-benzofuran (24 mg, 0.1 mmol), CuI (3.6 mg, 0.02 mmol), NaOt-Bu (28 mg, 0.3 mmol) and TBAB (6.4 mg, 0.02 mmol) in DMF (2 mL) was charged. The sealed vial was irradiated in the microwave for 1.5 h at 190 ˚C. After cooling, the reaction mixture was condensed in vacuo and purified by flash chromatography (CH₂Cl₂-MeOH = 10:1) to yield compound 8-(2,3-dihydrobenzofuran-6-ylthio)-9H-purin-6-amine (25 mg, 92%, Table [²] , entry 1) as a yellow solid.
Analytical Data
^¹H NMR (500 MHz, MeOH-d ₄): δ = 8.14 (s, 1 H), 7.24 (d, J = 7.6 Hz, 1 H), 7.07 (d, J = 7.3 Hz, 1 H), 6.97 (s, 1 H), 4.62 (t, J = 8.7 Hz, 2 H), 3.25 (t, J = 8.7 Hz, 2 H). ESI-MS: m/z = 285.9 [M + H]⁺. ESI-HRMS: m/z [M + H]⁺ calcd for C₁₃H₁₂N₅OS: 286.0763; found: 286.0768. HPLC analyses were performed on a Waters Autopurification system with PDA, MicroMass ZQ and ELSD detector and a reversed-phase column (Waters X-Bridge C18, 4.6 × 150 mm, 5 µm). The mobile phase was the mixture of 5-95% MeCN-H₂O with 0.1% TFA having a flow rate at 1.2 mL/min for 12 min; t _R = 7.47 min; purity, 99%; HRMS data were collected using Waters LCT Premier XE.