Aerobic Oxidation of Sulfides with a Vitamin B2-Derived Organocatalyst

Yasushi Imada; Itoko Tonomura; Naruyoshi Komiya; Takeshi Naota

doi:10.1055/s-0033-1339276

Synlett, Table of Contents

Synlett 2013; 24(13): 1679-1682
DOI: 10.1055/s-0033-1339276

letter

Aerobic Oxidation of Sulfides with a Vitamin B₂-Derived Organocatalyst

Yasushi Imada*

^aDepartment of Chemistry, Graduate School of Engineering Science, Osaka University, Machikaneyama 1-3, Toyonaka, Osaka 560-8531, Japan Fax: +81(6)68506222 Email: naota@chem.es.osaka-u.ac.jp

^bDepartment of Chemical Science and Technology, Institute of Technology and Science, The University of Tokushima, Minamijosanjima 2-1, Tokushima 770-8506, Japan Fax: +81(88)6567407 Email: imada@chem.tokushima-u.ac.jp

,

Itoko Tonomura

^aDepartment of Chemistry, Graduate School of Engineering Science, Osaka University, Machikaneyama 1-3, Toyonaka, Osaka 560-8531, Japan Fax: +81(6)68506222 Email: naota@chem.es.osaka-u.ac.jp

,

Naruyoshi Komiya

^aDepartment of Chemistry, Graduate School of Engineering Science, Osaka University, Machikaneyama 1-3, Toyonaka, Osaka 560-8531, Japan Fax: +81(6)68506222 Email: naota@chem.es.osaka-u.ac.jp

,

Takeshi Naota*

^aDepartment of Chemistry, Graduate School of Engineering Science, Osaka University, Machikaneyama 1-3, Toyonaka, Osaka 560-8531, Japan Fax: +81(6)68506222 Email: naota@chem.es.osaka-u.ac.jp

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Abstract

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Abstract

5-Ethyl-3-methyl-2′,4′:3′,5′-di-O-methylenedioxy-riboflavinium perchlorate (DMRFlEt⁺ClO₄ ^–) is readily derived from commercially available vitamin B₂ (riboflavin) and exhibits high catalytic activity for the oxidation of organic sulfides under an oxygen atmosphere (1 atm) with the assistance of hydrazine hydrate as a reductant. This is an inexpensive, convenient, and environmentally benign method for the selective oxidative transformation of sulfides into sulfoxides.

Key words

organocatalysis - aerobic oxidation - sulfides - sulfoxides - flavin catalyst

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References

References and Notes

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20 Aerobic Monooxygenation of Sulfides with Catalyst 1; Typical Procedure: A mixture of methyl octyl sulfide (40.1 mg, 0.25 mmol), NH₂NH₂·H₂O (12.5 mg, 0.25 mmol), and 1 ^16b (6.80 mg, 0.0125 mmol) in CF₃CH₂OH (0.25 mL) was stirred under an O₂ atmosphere at 35 °C for 3 h. The reaction mixture was extracted with CHCl₃ and the combined extracts were washed with brine, dried over Na₂SO₄, and evaporated under reduced pressure to give methyl octyl sulfoxide (41.9 mg, 95%) as a colorless solid.²³ Mp 38–39 °C [Lit.²⁴ 40.0–40.5 °C]. IR (KBr): 2999, 2953, 2924, 2848, 1675, 1472, 1419, 1300, 1080, 1027, 1001, 952, 722, 696 cm^–1. ¹H NMR (CDCl₃, 500 MHz): δ = 0.88 (t, J = 7.0 Hz, 3 H), 1.22–1.37 (m, 8 H), 1.38–1.53 (m, 2 H), 1.70–1.82 (m, 2 H), 2.56 (s, 3 H), 2.65 (ddd, J = 12.8, 9.1, 7.2 Hz, 1 H), 2.74 (ddd, J = 12.8, 8.8, 6.0 Hz, 1 H). ¹³C NMR (CDCl₃, 125 MHz): δ = 14.1, 22.6, 22.6, 28.9, 29.0, 29.2, 31.7, 52.5. HRMS (EI): m/z [M]⁺ calcd for C₉H₂₀SO: 176.1234; found: 176.1240.

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